A Textbook of Dairy Chemistry PDF
A Textbook of Dairy Chemistry PDF
A Textbook of Dairy Chemistry PDF
Volume One
THEORETICAL
A T E X T B O O K OF
DAIRY
CHEMISTRY
By
EDGAR R. LING
M.SC.(LQND.), F . R . I . C ,
A.R.C.S.
SECOND A N D REVISED
EDITION
REPRINTED
Volume One
THEORETICAL
fn(^
4' 4,
^
LONDON
First fublished
Reprintfd
Second and revised edition 'in two volumes)
(Volume 1)
1930
1934
1944
1946
BOOK
PRODUCTION
WAR ECONOMY
WITH
THE
OOMPLBTB
AUTHORISED
BOONOMY STANDARDS
1943
PREFACE
TO T H E F I R S T
EDITION
March imO
VOLUME ONE
THEORETICAL
CONTENTS
CHAPTEK
I.
II.
III.
IV.
V.
VI.
VII.
VIII.
PAGE
T H E CONSTITTTENTS OF M I L K
57
^
68
103
'122
144
CONDENSED M I L K AND M I L K P O W D E R
170
DAIRY
BY-PRODUCTS
AND
MISCELLANEOITS
SUBJECTS
184
NAME I N D E X
191
SUBJECT INDEX
193
CHAPTER I
THE
CONSTITUENTS
OF
MILK
00
o|
o
!>p:)
TS
o S
S
H
H
CQ
-p
t3
S
c3
to cS H "-'
<0
-5 d o
rt
^
m
pi
MHO
CO
i=l 1=1
o
O
43
03
pi
fe m
OQ
2 pi
<C
m
- 4)
O
3
CO
_ <u
^'S
t> o
2 >5
OQ - ^
C5
Lactose
Glucose
Galactose
Dilute mineral acids will also bring about this change. There is
still some difference of opinion regarding the presence of lactase
in milk, but if present at all, it has no great practical significance.
Certain varieties of yeast such as those present in Kephir
cultures are able to carry out the initial hydrolysis and to proceed
with the alcoholic fermentation of the two monosaccharose
sugars. This fermented milk contains small amounts of alcohol
(approximately 0-7 per cent), carbon dioxide, together with lactic
acid, and is occasionally prepared for special dietaries. I t is
claimed t h a t the casein of this product is in a very digestible
form.
Aqueous solutions of lactose reduce Fehling's solution and
ammoniacal silver nitrate solution, but after hydrolysis the
reducing power is doubled owing to the production of two active
reducing groups. Although insoluble in alcohol or ether, it readily
dissolves in hot acetic acid. Under slightly acid conditions lactose
may be oxidised to formic and Isevulinic acids (see page 105),
Butyric acid
phosphatase, an unidentified ether soluble substance, and a comt)lex of riboflavin^phosphoric acidprotein, which is known to
possess the properties of the Schardinger enzyme (i.e. it stimulates
the simultaneous reduction of methylene blue and the oxidation
of formalin when both of these are added to milk). However, the
physical condition of the fat determines to some extent the
precise composition of the protective layer, and in the case of
cream will modify its physical properties very considerably (page
126). I t is through the pecuHar properties of the adsorbed layer
that when metals like copper are dissolved in minute quantity by
milk they are able to stimulate oxidative changes in the fat
phase. The dissolved metal forms a metallic proteinate by direct
union with the globule surface protein, or it unites with the
plasma proteins and is then adsorbed by the globules. In either
case the water soluble metal is brought into direct contact with
the fat which otherwise would remain inaccessible. I n this respect
the globule surface material functions in a manner far from
protective. Palmer and his associates have pubhshed a number
of papers^ showing that it is possible to 're-surface' the fat globules
of milk and cream, but by so doing the fat is more vulnerable to
attack by various agencies leading to changes which will be
discussed under the heading 'fat deterioration.' The modern view
is thus far removed from the conception of the fat globule neatly
wrapped in an inert membrane. Indeed, the adsorbed layer is at
times the centre of vigorous chemical action.
The physical properties of pure fat extracted from milk, cream,
or butter, estabhsh it to be a mixture. Its colour varies considerably; it melts over a range of about 5C. and sets over a
similar range. Moreover, these two ranges do not coincide.
Hilditch^ gives 28-33C. and 24^19C. as the melting and setting
points. If the fat were just one compound, it would melt at one
definite temperature and sohdify at the same point. Taken
singly, some of the compounds present in milk fat would melt at
approximately 65C., while others would be liquid even at 0C.
There are many compounds which normally comprise milk fat
and each has its own melting-point and other distinctive physical
properties. On warming the sohd mixture it is the constituents
of lowest melting-point which first Mquefy. Some of the remaining sohds will dissolve in the liquid and wiU thus hquefy at a
,
Palmer et al., J. Dairy Sci., 1935, 18, 827 ; 1939, 22, 543; 1940, 23, 861.
^ T. P. Hilditch, The Industrial Chemistry of the Fats and Waxes, 1941, p. 134.
10
11
OOC.C17H35
CH2OH
CH - OOC.C17H36 + 3H2O == CH O H +
1
CH^ - OOC.C17H35
CHaOH
Stearin
Glycerol
3C17H36COOH
Stearic acid
OOC.C17H35
CHgOH
I
CH2 - OOC.C17H35
Stearin
2Ci7H35COONa + H^SO^
I
CH2OH
Glycerol
Sodium stearate
= 2C17H35COOH + Na^SO^
Stearic acid
12
Name
At
ordinary
temperatures
Volatility in
steam
Caproic
C7H15COOH
Caprylic
C9H19COOH
Capric
C11H23COOH
Laurie
C13H27COOH
Myristic
CzaHsiCOOH Palmitic
C17H35COOH
Stearic
C19H39COOH
Arachidic
Water
Solubility
Soluble
Slightly
soluble
Very slightly
1-0 Liquid Volatile
soluble
Very slightly
2-0 SoUd Volatile
soluble
Almost
2-5 Solid SUghtly
volatile
insoluble
10-0 Solid Very slightly Insoluble
volatile
Insoluble
25-0 SoUd Nonvolatile
Almost
10-5 SoUd Nonvolatile
insoluble
0-5 SoUd Non-volatile Insoluble
Decenoic
Dodecenoic 5-0 Liquid Nonvolatile
Tetra
Pecenoie
Oleic
33-0 Liquid Nonvolatile
Insoluble
Insoluble
13
CH (Palmitic)
CH (Palmitic)
CH (Oleic)
CH (Stearic)
CHa (R)
CHa (Stearic)
CHj (Palmitic)
CHa (R)
; where R. denotes one of the lower fatty acids. Of these four,
group A is the most common.
2. A number of molecules are fully saturated.
3. The Palmitic radical is present in some 75 per cent of the
I molecules.
I As the actual percentage of each acid is subject to some
f variation, one must expect their distribution in the various
; glycerides to show similar variation. Arising out of the extensive
, research on the chemical constitution of the glycerides, the
1 Analyst, 1928, 53, 641.
14
15
2 Ibid., 231.
16
II.
00
or = C : C = CH(0H)C0
OH OH
The peculiar flavours and odours of oxidative taints may be
caused by the peroxides or such decomposition products as
epihydrinaldehyde, which is the substance reacting with phloroglucinol in the Kreis test for oxidised fat. Hilditch* suggests
that this substance may be derived from linoleic acid by the
following reactions.
RjCH: CH.CHa.CH : CHR2+2O2 = = RjCH CH.CH2.CH CH.Ri,
o0
CHO.CH2.CHO =
00
= = RiCHO+R2CHO+CHO.CH2CHO.
CH(OH) : CH.CHO = = CH^ . CH . CHO
Epihydrin aldehyde
1 W. L. Davies, J. Dairy Bea., 1932, 3, 254; Krukovsky and Sharp, / . Dairy Sci.
1940, 23, 1119.
2 W. L. Davies, Chemistry of Milk, 2nd edit., p. 81.
Bills, / . Soc. CUm. Ind., 1926, 45, 193.
* Hllditch, The Industrial Chemistry of the Fats and Waxes, 1941, 325.
17
18
19
20
21
CH (OOCR2)
CH2 - 0 - P - 0 -7 C H , - -CH^
/ \
0 OH
N (CH3)30H
Rj.COOH
R2.COOH
HO-P-OH
/ \
0
OH
Fatty acids
Phosphoric acid
CHaOH.CH2.N(CH3)30H
,
Choline
22
Milk
.
Separated
milk
Cream (41 per
cent fat)
Buttermilk .
Butter .
Whole milk
powder
Heinemann*
Rewald*
Holm et al^
Per cent
Per cent
Per cent
0-035 - 0-036
0-0314
0-0337
0-015 - 0-018
0-0169
0-114 - 0-126
0-153 - 0-212
0-1816
0-1872
0-1819
0-24
23
24
(1)
(3)
(2)
"CHi
CH,
/CH3
A'^
CHCH
CHi
H,C
CH,
/ = \
H^C
H
.CH
V/
CH-
CH,
-CH,
CH
CH,
o,r Xrf/ ^ d ^
While the general configuration of the sterols is the same, they
differ in the number and position of their double bonds. They
are, in fact, outstanding examples of the manner in which sKgM
alteration of the ornamentation around the original design may'
1 Daries, 1936, J. Dairy ScL, 7, 14.
25
^"'
53
6
;^u
u_-u
27
28
CH,
^-"3
CH3
CH3 t
dH3
CH,
^ C
I
I
1
I
, . (,y^ ^C-C3i-.CH-C-.CH-CH:CH'C:C3i-CH;CH'CH:C-CH:CB'CH:C'CH:ar-C''
ML
CJI3
C ' '" " 0*221126
HaC
^C-CHa
'^CH,
CH2
CH3
CHi
II
I I
(3 C a r o t e n e C ^ Q H J S
H2C
CM,
CH,
CHa-
y ^
+ 2H9O
CH5-C^^CH2
CH2
CH2
(3 C a r o t e n e
CH^
'^V,
I
I
H2C''
^C-dH:dH-C:CH-CH:CB-C:CH:'CH20H
-^2
H^C^
^CCHi
^CH2
CH3
H7C
CHa
/
CH5
CC22H26~~~^H
HjC^ ^C-CH3
CHj
CH2
C3l3-C^
CH2
Vitamin A
.Ctti
CH
ct C a r o t e n e CI40H56
CHi
HjC
CHi
CH3
C C22H26
V"
C-CHa
CIHT-C
OH
Xanthophyll ^401154 (0H)2
^dHj
30
Gross
))
average
Winter
Shorthorn;
Carotene
Vitamin A
0-27
0-68
0-25
0-58
Ayrshire:
Carotene
Vitamin A
0-36
0-85
0-27
0-66
Priesian:
Carotene
Vitamin A
0-40
0-90
0-35
0-61-
Guernsey:
Carotene
Vitamin A
0-92
0-75
0-73
0-54
Summer
Ratio Vit. A/
Carotene
0-29
0-84
2-5
0-41
1-18
2-4
0-47
1-21
2-25
M4
0-95
0-80
1
1
1939
Gviernsey
Jersey .
Ayrshire
Holstein
Herd
.
I
>
j
1
13
25
11
20
72
Summer
Range
Average
Samples
4-68-12-0
4-15-11-5
1-93- 9-59
1-45- 9-42
1 45-12-0
8-5
5-87
4-27
3-49
5-42
13
21
8
17
62
Range
| Average
31
I
95 Protein (3-18)
78-5 Casein
(2-63)
9-2 Albumin
(0-31)
5 Non-protein
3'3 Globulin
(0-11)
4-0 Proteose-peptone
(0-13)
32
= NH2CH2CONHCH2COOH + HgO
Glycyl glycine
33
'
Casein ! 53-5
Albumin i 52-51
Globulin 1 51-88
"
Hydrogen
Oxygen
Nitrogen
Sulphur
Phosphorus
7-13
7-10
6-96
22-14
23-04
24-62
15-8
15-43
15-44
0-72
1-92
0-86
0-71
0-24
35
form salts with both acids and bases, its acid nature predominates
in milk. I t combines with sodium hydroxide to form sodium
caseinate, and is sufficiently acid to liberate carboP dioxide from
calcium carbonate. The base-binding powers have been estimated
as approximately 9 ml. N/10 NaOH per gm. casein. I t has been
suggested t h a t some at least of this acidity may be attributed to
residual acid groups of the phosphoric acid molecule.^ I n cow's
milk casein is united to calcium, but the acid properties are only
partially nullified thereby, the resulting compound being an acid
calcium caseinate or more correctly, calcium hydrogen caseinate.
Although there may be certain theoretical objections to this
picture of the casein molecule as it exists in milk, it does help the
student to understand the chemical reactions of casein in milk
and dairy products.
Like all acid salts, the residual acid may be neutralised by the
addition of a base. The addition of sodium hydroxide to milk
will therefore neutralise calcium hydrogen caseinate in the same
way as its addition to a solution of acid sodium phosphate will
result in the formation of the base saturated tri-sodium phosphate.
Calcium acid caseinate + NaOH=Calcium - sodivim- caseinate
+ Water
It must follow therefore, that when titrating milk with sodium
hydroxide as in the customary acidity test, sonie of the solution will be used to neutrahse casein, quite irrespective of the
presence or absence of lactic acid. The author has found that the
acidity of casein as it exists in milk amounts to approximately
0-32 ml. of N NaOH per gm. of casein.^ On this reckoning about
one-third of the acid groups of casein are normally free in milk.
It is well known that as lactic acid develops in milk, there is a
gradual migration of calcium from the colloidal to the soluble
condition, and that this process continues until the sample
curdles. There are two reactions which account for this enrichment of the soluble phase at the expense of the colloidal, one
which is the removal of calcium from calcium hydrogen caseinate
to form calcium lactate according to the equation :
Calcium hydrogen caseinate + Lactic acid
>
'
= Acid casein + Calcium lactate
Colloidal
Precipitate
^ R. A. Gortner, 1938, Outlines of Biochemistry, p, 481.
2 E. R. Ling, 1937, J. Dairy Res., 8, 173.
Soluble
36
3K2 oxalate
Neutral
3Ca oxalate
Precipitate
2K3PO4
Alkaline reaction
3'?
Soluble
Soluble
38'
into the whey, while the other two are coagulated. The significance of this finding will be better appreciated when considering
the action of rennet on milk, but it may be stated here t h a t the
conception of rennet attacking casein by releasing the soluble
fraction and precipitating the remainder is one which opens up
an entirely new field of study.
The solubility of casein in various solvents is also a matter of
industrial importance in the preparation of casein glues and
cements. As early as the eleventh century a water-resistant glue
was made from mixtures of curd and hydrated lime. I n borax
solution casein dissolves to form a glue which possesses many
advantages over bone glue. Sodium hydroxide solution dissolves
casein to give sodium caseinate, which may be forced through
fine jets into a precipitating medium whereby casein fibres are
obtained. Casein textiles known as Lanital are comparatively
new and their future development will be followed with keenest
interest.
Great interest is also shown in the development of casein
plastics, which have found their way into thirty or forty trades,
and from which such famiUar articles as buttons, insulating
panels, fountain-pen barrels, umbrella handles, piano keys, knife
handles, combs, knitting needles, etc., are frequently made. I t
must be emphasised, however, t h a t casein is only one member of
a growing list of substances named plastics. In the late nineteenth century it was discovered that casein reacts with formaldehyde to produce a new compound possessing properties very
distinct from those of the parent material. I t is considered that
the reaction concerns the free NHg groups of the protein, although
the precise mechanism of the reaction is still obscure. The
treatment renders casein much more resistant to water, acids
and heat.
Although the raw material for casein plastics is rennet casein,
it is possible to prepare them from acid precipitated casein, but
owing to lower production costs, the former is generally used.
The dried material is ground to the requisite fineness, coloured,
mixed with the minimum amount of water and subjected to heat
and pressure. As a result of this treatment the substance softens
and may be extruded from machines in the form of rodding or
tubing. Sheeting may be made by hydraulic pressure on the
heated rods. The material is then hardened b y immersion
in 4-5 per cent formaldehyde for varying lengths of time,
39
40
41
42
Rennet
Heat
.
.
. Coagulated
Coagulated
above 100C
Albumin
Globulin
Not
coagulated
Not
coagulated
Not
Precipitated precipitated Precipitated
Precipitated.
Excess magnesium
phate
Not
Precipitated precipitated Precipitated
(unless acid)
sul-
Not
precipitated
Not
precipitated
43
44
K,0 .
CaO .
NagO.
MgO .
P2O5 .
0-190
0-176
0-068
0-018
0-233
0-106
CI
Citrate ex] jressed
as citric acid
0-18
Fe
.
1-2 parts per
million
Cu .
0-12 parts per
million
I
0-02-0-14 parts
per million
Minimum
Maximum
0-202
0-166
0-076
0-148
0-126
0-050
0-217
0-212
0-155
0-229
0-111
0-166
0-068
0-291
0-163
CoUoidal (0-121%)
[approx. 2/3]
combined with casein (0-037%)
[approx. 2/9]
46
Organic (0-094%)
[approx. 2/5]
Insoluble
(0-077%)
[approx. 3/10]
Soluble
(0-086%)
[approx. 3/10]
Insoluble
(0-049%)
[approx. 1/5]
Soluble
(0-045%)
approx. 1/5]
,
*
Matticki
Wardlaw^ .
Lampitt et al. ^
Calcium
Phosphorus
Magnesium
Per cent
Per cent
Per cent
24^30
30-40
25-^2
29-39
35-55
40-58
62-83
46
47
the absence of something was one which the human mind could
not readily conceive. Nevertheless the view that faulty feeding
could have such disastrous results was slowly evolved and cul-"
minated in the pioneer work of men like Lunin, Funk, Stepp,
Pekelharing, Hopkins, Osborne, Mendel, McCollum, and Davis.
I n this country the experiments of Hopkins conducted in
1906 demonstrated the function of vitamins in nutrition. Selecting a batch of young male rats he fed them on a carefully purified
diet of lard, casein, starch, sugar, mineral matter and water.
These items were correctly balanced, and according to the
accepted standards of the day the ration could be considered
adequate. The rats failed to make satisfactory growth, and soon
began to lose weight and condition. At this stage the inclusion in
the ration of 2 ml. of milk produced phenomenal results. The
rats showed immediate recovery and growth proceeded at the
normal rate. On the other hand, a continuance of the chemically
pure diet resulted in the death of the animals. This and many other
experiments by Hopkins and other workers brought the conviction
that a complete diet must contain substances hitherto unrecognised,
other than fats, carbohydrates, proteins, mineral matter and water;
and that these vital factors were present in whole milk.
Since these pioneer experiments were performed, research in
the subject has been directed to the problem of isolating these
various factors from common foodstuffs, studying their physiological functions and chemical nature, and to the possibihties of
their synthesis in the laboratory or on a commercial scale. When
the chemical nature of these vital factors (now known as vitamins)
was obscure they were named "fat-soluble A," "water-soluble B , "
etc., but now t h a t their chemical constitution is known, it is
hoped that they will be called by their chemical names, particularly as the alphabetical system is not universally the same. As
these notes are being written in the transition period, it will be
necessary to use both systems.
The vitamins present in milk are:
Fat-soluble A, D, E (Tocopherol).
Water-soluble B^ (Anexirin or Thiamin).
Bj (consisting of Riboflavin, Nicotinic acid,
IPantothenic acid, Pyridoxine or Adermin),
C Ascorbic acid.
In considering the milk vitamins it becomes necessary to
distinguish between those which are merely present and those
48
49
yolk, green foods, and .carrots. Most oils from oil seeds are
deficient in this vitamin, a serious matter to the margarine manufacturer, who uses these oils extensively. Concentrated preparations of vitamin A are now available and these are incorporated
in margarine to maintain the product at a steady all-the-year
level; indeed, in the Second World War this was z'equired by law.
Contrary to earlier views, vitamin A is fairly heat stable,
neither pasteurisation nor sterilisation causing any appreciable
reduction in quantity. Similarly, condensation and drying are
without effect. Being highly rmsaturated compounds, vitamin A
and carotene are susceptible to oxidation. When butter fat undergoes oxidation the natural colour of the carotene is simultaneously
bleached. For this and other reasons it is desirable in any form
of milk processing to reduce risks of oxidation to a minimum.
An interesting circumstance arises from the vitaminisation of
margarine. Unless determined efforts are made to improve the
winter feeding of the dairy cow, winter butter will compare
unfavourably in vitamin A potency with vitaminised margarine.
With the rapid disappearance of public prejudice against margarine there is hkely to be a hvely competition between the two
industries unless steps are taken to improve the winter milk.
Vitamins of the B Group.Water-soluble B was originally
considered to be one substance, but it was later resolved into two
sections, one heat labile (B^), and the other heat stable (Bg). The
process of fractionation continues, and we now recognise vitamin
Bg as a mixture of a number of vitamins. As the position is still
rather confused, the student will find the following diagram useful.
The original water-soluble B
Heat labile (Bj or Aneurin or Thiamin)
Anti-beri-beri
Anti-polyneuritis
-
50
1T=
CK,~C
^ CNH/HCl
k^\
C"CH2^N
C = C
CHCH2
NCH
CH
S
OH
about 0-06 mg. per cent, and later milk between 0-03-0-04 nig.
per cent. There is thus a rapid decline during early lactation.
Season and feeding appear to be without effect. ^ Richer sources
of this vitamin are the whole cereal grain, eggs and yeast. Being
situate in the germ or adjacent layers, thiamin is to a large extent
removed from the cereal grain during the process of milling in
which a white flour is the aim. Thus it becomes necessary in time
of war either to produce a white flour which must be enriched
with vitamin preparations or to insist upon the milling of flour
which contains sufficient "bran" to ensure a reasonable supply
of thiamin.
Riboflavin.[Vitamin 0 in America).This compound is
identified with the green yellow pigment of whey, and is also
known to exist as a phosphoric acid-riboflavin-protein complex
to which reference has already been made. It is considered that
one-tenth of the 0-1 mg. per cent of riboflavin in milk is bound
to protein. 1 There is a higher concentration in colostrum (0'40-4 mg. per cent), but the level decHnes very rapidly to the normal
for milk. The quantity in milk appears to rise under summer
feeding conditions. The possibihty of this substance being synthesised like thiamin in the rumen must not be overlooked.
Riboflavin is also present in liver, kidney, eggs, and green foods.
> Houston et al, 1940, J. Dairy Res., II, 145.
51
Amongst its many functions,' it is a growth-promoting healthstimulating substance which is strongly identified with oxidationreduction changes where it plays the role of a catalyst or a
co-catalyst. I t is obviously a substance of vital importance in
CHi-CHOH-CHOH-CHOH-CHpH
CH,C^ \ C ^ ^C^
^CH
^N^
\co
^C6
OH
^ ^ - ^
-:C
CH
II
^ ^C-COOH
^ r'r-^v rivs
CH
^C-rt-^MH.
^C-OONHj
OH-C
<C-CHpH
'
Pyridoxine
62
53
rCO
CO
CHO
CHO
CH
CO
Oxidation
-
CO
I
I
CH
Reduction
CHOH
CHOH
capn
CHjOH
54
CH,
C
CH-Cs.
CH,
CHj
CHj
I
I
_{CH,)-CH-(CHjVCH-rcH2)-CH-(GH3),
C..
C^
I
CH
^O
CH,
55
wheat germ oil, and green leaves, but it is also present in a wide
variety of foods, including milk and meat.
The following table gives a general summary of the distribution
of the common vitamins in milk and dairy products.
Bi
Fair-Good
Fair-Good
Pair-Good
Good
Very fair
Slight
Very slight
SUght
Good
Good
SUght
Good
Shght
Pair
Absent
Very fair
Good
Very fair
Absent
Good
Good
Good
Slight
Slight
Slight
SUght
Very fair
~
Very fair
Slight
Very slight
Slight
Very fair
Very fair
Very fair
Fair
B.
Good
Good
Good
Good
Fair
Fair
Pair
Gases Present, in Milk.^As drawn from the udder, milk contains about 8 per cent by volume of dissolved gases among which
carbon dioxide predominates. In contact with the atmosphere
this amount falls to approximately 6 per cent, but the change is
not merely one of quantity. There is a significant alteration of
composition as the milk gases reach equilibrium with those of the
atmosphere. Carbon dioxide is lost and oxygen and nitrogen
gained, as the figures in the table will show.
CHANGES IN COMPOSITION OF DISSOLVED GASES AS MILK REACHES
EQTTELIBRIUM WITH THE ATMOSPHERE
-v
Oxygen
Nitrogen
Carbon
dioxide
Total
Per cent
0-092
Per cent
jl-184
Per cent
6-577
Per cent
7-853
047
1-29
4-45
, 6-21
56
OHAPTBK II
58
59
60
61
62
63
should be no further change once the sample has aged; unless the
changes in casein are of a reversible nature.
The subject has been regarded as one of academic or historic
interest and for many years was neglected. I t has recently come
into prominence again through the work of Boden and Campbell, ^
who found t h a t the new density formula gave lower values for
non-fatty soHds than the old lactometer formula of Richmond.
The discrepancy is of the order 0-2 per cent. Richmond's
formula was put forward for samples in which the Recknagel
phenomenon was complete, whereas the modern formula is used
for milks warmed to 40C. and then cooled to 20C.^ in which
the phenomenon would be absent, since presumably the fat would
be liqmd. The modern density hydrometer formula is calculated
from Richmond's with no correction for the Recknagel change,
and Boden and Campbell suggest this as one reason for the
observed discrepancies. This is a practical subject of great importance, and it may be necessary to amend either the modem
formula or the technique as at present prescribed.
That changes in the physical condition of the fat are partly
responsible for the Recknagel phenomenon there can be Uttle
doubt; but the work of Pyenson and Dahle^ on bound water in
milk and dairy products leads to the conclusion that, as originally
suggested, changes in casein are also partly responsible.
Bound Water.Water is present in milk to the extent of about
87-6 per cent, but it is not all in the free condition. Some is firmly
bound by the milk proteins, some by phospholipids, and some by
the substances adsorbed on the fat globules. The quantities bound
in milk and some dairy products are shown in the following table.*
Product
Raw milk
Skim milk
Cream 1
2
Buttermilk
Colostrum
.
.
.
.
.
Age
m
hours
Total water %
Water bound
per 100 gms.
of product
24
24
8
8
24
86-75
90-56
70-92
56-80
91-75
80-83
3-18 gms.
2-13
2-5
3-42
1-75
4-65
64
. Product
R a w milk .
,
R a w skim milk .
gravity
Aged at 40"?. Specific
at 60F.
0 hours
8
24
24
1-0314
1-0328
1-0332
1-0359
1-0366
1-0371
% Bound
water
2-79
2-98
3-18
1-81
2-05
2-13
65
66
67
CHAPTER I I I
T H E COMPOSITION OF M I L K
PREVIOITS chapters have dealt primarily with the quaHtative
aspect of milk composition, but on several occasions it became
necessary to refer to the variations in concentration shown by
certain constituents. These variations make it difficult to assess
the quantitative composition of milk. There is only one approach
to the problem, and that is to analyse large numbers of samples
taken from different herds of different breeds in various parts of
the country and over different periods of the year. When the
results are converted to mean values an 'average' composition is
obtained. By this means factors such as individuality, breed,
stage of lactation, season, etc., which are known to influence the
composition of milk, are damped down or practically ehminated. Even so, the, question might be raised, "Of what use
is this average when most practical problems are concerned with
the milk of localised herds of perhaps ten to forty cows?" It
is often emphasised that the 'average' man is non-existent.
Whether this contention might apply to milk is a matter
which the author hopes will become apparent in the treatment
which follows.
Regarding the number of samples necessary to enable an average
to be calculated, no hard and fast rule can be laid down, but
most investigators have worked on a minimum of some 700.
Some have taken individual samples, while others have taken
bulk samples with no record of the number of cows in the herds.
The problem of giving published data their correct assessment
may be illustrated by the following example. An investigator 'A'
analyses 1,500 samples of mixed milk from one herd of twenty
cows, and another, 'B,' takes 15 samples from each of 100
diii'erent herds, none of which contains less than 10 cows. Both
have analysed 1,500 samples of mixed milk, but are their results
comparable? In the author's opinion they are not. Investigator
'A' spreads his work over more than two years and his results
refer to a very varied set of seasonal conditions, whereas 'B' is
able to complete his work in a much shorter time. Another
important difference lies in the fact that 'B' has obtained his
68
69
results from very many more cows. Both have their intrinsic
merits. The results obtained by ' B ' would give a more valuable
estimate of the average composition of milk, but in many respects
the work of 'A' is of greater practical value in demonstrating
day-to-day fluctuations in composition, lactation effects, seasonal
variations, and general management factors, such as are commonly manifest in a herd. Both tjrpes of investigation will be
encountered in a search through the Hterature of the subject.
In this matter the student must acquire the habit of critical
reading, or at least should be able to exercise discrimination so
as to avoid coming to conclusions which the investigators never
intended.
Average values alone are of very Mmited use. *'In an investigation
into the composition of milk, Cranfield, Griffiths, and Ling^
examined 732 samples of mixed milk from 15 herds, corresponding
to some 418 cows. The average percentages of fat and non-fatty
solids were 3-71 and 8-75 respectively. But much more information was required. At the time of the investigation questions
were being asked such as: "What is the extent of variation on
either side of the mean composition of genuine milk?" or "What is
the likelihood of genuine milk falling down the legal presumptive
limits of 3-0 per cent fat and 8-5 per cent non-fatty solids?" The
mere statement of average values is not enough ; the distribution
of the results each side of the mean values being of equal
or perhaps greater importance. From the distribution of the
fat percentages it will be seen that although the mean was 3-71,
there were sixty instances out of 732 (i.e. 8'2 per cent) in
which the values fell below the 3 per cent limit, and that more
than 4 per cent fat was shown in 206 instances (i.e. 28 per cent
of total).
1 Cranfield, Griffiths, and Ling, 1927, J. Agric. Sci., 17, 62.
70
FAT
Range
per cent
2-20-2-39
2-40-2-69
2-60-2-79
2-80-2-99
3-00-3-19
3-20-3-39
3-40-3-59
3-60-3-79
3-80-3-99
4-00-4-19
4-20-4-39
4.40-4-59
4-60-4-79
4-80^-99
5-00-5-19
5-20-5-39
5-40-5-59
6-60-5-79
5-80-5-99
S.11.E
No. of
samples
Eange
per cent
No. of
samples
3
8
12
37
67
96
99
112
93
83
44
31
21
7
10
4
3
1
1
7-90-7-99
8-00-8-09
8-10-8-19
8-20-8-29
8-30-8-39
8-40-8-49
8-50-8-59
8-60-8-69
8-70-8-79
8-80-8-89
8-90-8-99
9-00-9-09
9-10-9-19
9-20-9-29
9-30-9-39
9-40-9-49
9-50-9-59
.
1
3
5
13
26
59
103
107
113
116
80
47
33
17
7
1
1
732
Mean % of fat, 3-71
'
732
Mean % of S.ri.F.,, 8-746
(>q
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72
Rich- Elsdon^
mond^
%
Water
Fat
Protein
Other nitrogenous
substances
Lactose
Ash .
Other substances
Total
P2O5
CaO
87-34
3-75
3-40
0/
/o
% S.D.
87-26 87-64
3-75 3-71 56
3-20 3-25 - 1 8
4-70
0-75
0-06
0-20
4-70
0-75
0-15
100-00
100-00
0-22
0-15
Cranfield,
Griffiths,
Ling*
4-74 (diiJ.)
0-76[-025
Tocher^
S.D.
/o
87-19
3-95 + -78
3-17
0-35
4-64 +37
0-70 + -05
Van
/a
Davies d al.
A.M. milk
87-1
3-9
3-2
87-84 S.D.
3-28 -265
3 0 0 -134
0-20
4-87 163
5-1
0-7
1
100-00
10000
0-234 -018
0-184 -013
100-0
S. D.=Standard deviation.
73
Per cent
Water
.
.
.
.
Fat
. . .
.
Casein
Albumin
Globulin
Proteose peptone .
Other nitrogenous substances
Lactose
Ash
.
87-54
3-71
2-63 1
0-31
O-Il
0-13
0-11
4-70
0-76
Protein 3-18
100-00
Variations in the composition of Milk.Before considering
the various factors known to influence the composition of milk,
it is well to recognise that some constituents and some physical
properties show much less variation than others. These differences
are clearly demonstrated in the table which gives the coefficient
of variation for several constituents as calculated from the works
of Tocher^ and Cranfield, Griffiths, and Ling.^
COBBFICIENTS 0 VARIATION
Non-fatty solids
Ash
.
.
.
.
Lactose
Total nitrogen .
Casein nitrogen .
Pat .
Albumin nitrogen
Yield per milking
Yield of fat per milking
Tocher
Cranfield, Griflfiths
and Ling
5-02
7-21
8-01
12-22
13-68
19-76
20-00
36-53
38-44
2-75
3-29
5-54
15-1
Standard deviation
X 100.
Mean
74
10
247
165
116
84
62
46
34
26
19
15
11
12
13
14
15
16
17
18
19
20
11
75
%Pat
Daily variation
No. of
/A.M.
occasions \ P.M.
0
5
3
2
8
8
1
16
12
3
5
6
4
4
5
5
0
3
6
0
1
% Non-fatty solids
Daily variation
No. of
/A.M.
occasions \ P . M .
0
2
6
1
7
8
2
6
6
3
6
7
4
9
1
5
2
4
6
2
1
7
2
4
8
2
0
9
0
1
Cranfield,^ from a study of 359 a.m. and 362 p.m. samples from
a herd of 30-35 cows over a period of one year, observed the
following variations.
DAILY VABIATIONS
Non-fatty solids
Fat
Over 0-5%
Over 0-75%
Over 0-5%
Over 0-75%
/A.M.
VP.M.
11
N u m b e r of
occasions
76
No. of No.
days of
oftest cows
Elsdon^ and
Stubbs
.
134
40
6
4
5
5
2
2
2
0
0
0
0
0
0
0
Lauder^ and
Fagan
70
20
0
2
3
6
1
2
4
0
0
0
0
0
0
0
Gariorth^
report
52
18
No. of
times
Ekdon* and
Stubbs .
2
5
2
2
12
60
Tocher*
21
7
6
3
3
0
1
1
0
No.
No.
of/A.M.
times \ p . M .
2
2
6
4
1
3
"
77
from selected cows of the various breeds, while others refer to milk
obtained under the abnormal conditions pertaining at shows. By
far the most comprehensive figures available in this country refer
to the fat content of the milk of various breeds, as determined
under the Butterfat testing scheme of the Ministry ofAgriculture.^' They are summarised in the table.
F A T PEECBNTAGB OF THE M I L K O F V A R I O U S B R E E D S
Year ending
Oct. 1, 1936
4-5%
5-6%
Over
6%
Jersey .
47
733
913
135
1828
5-05
1687
5-04
Guernsey
329
1957
791
33
3111
4-61
2831
4-61
Ayrshire
989
448
1448
3-81
1133
3-78
Lincoln Red .
142
38
181
3-72
174
3-62
Red Poll
42
622
161
828
3-64
694
3-62
Shorthorn
102
2139
361
2606
3-62
2744
3-58
Friesian
543
2652
157
3353
3-29
3153
3-26
Others .
87
87
178
3-97
191
3-92
Totals .
695
7007
3942
1720
169
13533
3-93
12597
3-89
78
E-oadliouse
Vieth'
Overman'
10-1
9-98
10-1
10-05
10-05
10-15
9-79
9-44
10-03
10-2
8-90
9-17
8-73
9-42
9-28
8-78
9-38
9-24
9-28
9-25
9-34
Drakeley"^ Tocher^
Jersey
Guernsey
Kerry
Dexter
South Devon
Ayrshire .
Red PoU
Shorthorn
Lincohi Red
Friesian .
9-82
9-78
9-51
9-51
9-63
9-37
9-45
9-40
9-35
9-12
79
on the non-fatty solids is purely mathematical, and if the percentages are calculated on a fat-free basis it disappears entirely.
Davies^ illustrates these effects from data obtained at the National
Institute for Research in Dairying.
COMPOSITION OF A.M. AND P.M. MILK. DAY INTERVAL 9 HOURS
NIGHT INTERVAL 15 HOURS
A.M. Milk
Period
1928-9 .
1929-30 .
1930-1 .
1931-2 .
1932-3 .
Whole period .
No. of
samples
Pat
352
365
336
363,
120
1565
3-28
3-21
3-22
3-27
3-38
3-25
%S.n.F.ona
fat free basis
P.M. Milk
% No. of
S.n.F. samples
8-99
8-87
8-98
8-99
8-78
8-94
337
365
365
365
118
1550
0/
Pat
S.n.F.
A.M.
P.M.
4-69
4-55
4-46
4-53
4-39
4-54
8-84
8-84
8-84
8-87
8-77
8-84
9-30
9-16
9-28
9-30
9-09
9-24
9-28
9-26
9-25
9-29
9-17
9-26
Cow
Cow
Cow
Cow
Cow
1
2
3
4
5
.
.
.
.
.
3
5-30 a.m.
milking
Difference 2-3
lbs. F a t
4-70
4-65
4-25
5-25
4.75 j
-0-24
+0-14
+0-06
^0-18
+0-21
0-59
0-67
0-83
0-97
0-88
4-35
5-60
4-70
4-50
5-20
0-44
0-64
0-68
0-56
0-76
0-68
3-25
2-75
0-50
2-30 i 0-62
2-65 i 0-74
2-20 ! 0-55
MO
2-86
2-40
1-85
3-00
80
81
1st milking
2nd
3rd
4th
%Total
soKds
Fat
/o
%Total
protein
Lactose
Ash
/o
SG
24-55
18-0
16-79
16-21
3-89
3-84
3-11
3-82
16-76
9-33
7-06
6-16
2-50
3-52
3-85
4-23
1.33
0-97
0-96
0-88
1-0604
1-0437
1-0376
1-0372
0/
/o
0/
Elsdon^ has determined the freezing-point depression of colostrum and finds it to be greater than that of normal milk. As the
1 Gaines, 1928, Bull. 308, Illinois University.
2 Garnett and Overman, 1940, J. Dairy Sci., 23, 13.
.2 Elsdon, 1934, Analyst, 59, 665.
82
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84
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86
88
89
Two carefully controlled erperiments on the effects of starvationi 2 have brought to light the following facts. Under these
conditions there is a reduction of yield and percentage of lactose
while the fat, protein and non-fatty solids show increased concentration. Smith^ observed that when the lactose fell to an
abnormally low percentage, some unidentified compound was
secreted which partly restored the osmotic pressure. During the
course of this work it was noticed t h a t the composition of the
milk fat was profoundly altered. Oleic acid increased very considerably at the expense of the lower fatty acids. On a molecular
basis the increase of 19 molecules of the former was offset by a
decrease of 24 of the latter. Incidentally this observation supports
the view that normally the lower fatty acids are produced from
oleo glycerides of the blood.
Under less drastic conditions of malnutrition similar increases
in the unsatnration of milk fat were observed b y Hiddet el al.^
These workers reduced the production ration to one half the
required level. A reduction of yield was observed together with
a fall in per cent non-fatty solids (0-3-0-5) which was felt mainly
in the protein fraction.
Age.The most recent extensive work on the effect of the age
of the cow on the composition of milk has been carried out by
Bartlett,* whose principal observations are summarised in the
following table. As already observed (page 82), this factor may be
more potent in advanced lactation.
Number of Lactations
No. of cows
Relative
yields
67
67
49
34
21
12
100
116-6
133-4
143-7
151-8
151-9
156-3
141-4
111-6
F a t per cent
3-95
3-90
3-90
3-84
3-79
3-70
3-74
3-67
3-74
S.n.F. percentage on
the fat-free
milk .
940
9-32
9-26
9-21
9-10
8-98
903
8-94
8-88
90
Ibid.
" Petereen, 1942, J. Bctky Sei., 25, 7},
91
92
but not identical with natural oestrogen, and being much cheaper
has been used in a number of these experiments. The stimulating effect has been obtained by injections of this compound,
or by gentle massage of the udder with an ointment containing
1 per cent of the di-propionate of di-ethyl-stilboesterol. I t is,
however, more difficult to separate the two effects with the
synthetic preparations than with the natural oestrogens. These
experiments have also led to the conclusion that oestrogen
stimulates the lactation hormones of the pituitary gland.
I n conclusion it must be emphasised t h a t the subject is still in
experimental stage and must at present remain in the hands of
expert animal physiologists.
93
94
soluble ash was abnormally high and it seems again that the
composition was modified in much the same manner as occurs
with mastitis. I n March 1927, tuberculosis was diagnosed,
although a veterinary examination in J u n e 1925 failed to establish any abnormality. The cow was slaughtered in July 1927,
having been seriously ill since June of t h a t year. Post-mortem
examination revealed extensive tubercular lesions of the
right lung. The disease was also very evident in the right hind
quarter.
The reader may be impressed by the number of factors which
are known to influence the composition of milk, and may imagine
that when a herd gives milk of abnormal composition, the cause
may be traced to one or more of these influences. Such is not
always the case. The author has had occasion to examine the
possible cause of a herd giving persistently low percentages of
non-fatty soHds with the negative result t h a t none of the known
factors could be held responsible. Other similar experiences are
recorded in the literature, one of the most noteworthy being t h a t
of Lesser. ^ I t may be that on occasion milk suffers from the physiological change in which substantial reductions of lactose are but
shghtly counterbalanced by small increases in chlorides. Even
so, there is no known reason for this change nor is there any
proved method of rectifying the condition. I t may be the result
of unbalanced hormonal control as was suggested by Kay, but
it must be admitted that at present our knowledge is far from
complete.
95
The sample is divided into three parts and the bottles sealed.
One is intended for analysis, one is handed to the vendor or his
representative, and the remaining one is retained by the local
authority for submission to the government analyst in the event
of any discrepancy between the certificates of the pubUc analyst
acting for the local authority and any independent analyst to
whom the vendor has entrusted his own sample.
When a sample is known to originate from any particular herd
of cows, the vendor may within 60 hours request the local
authority to obtain a sample from a corresponding milking, it
being understood t h a t the cows are efficiently and fully milked
and that no changes in milking intervals are made. This sample
is known as the appeal sample and is sometimes taken at the
request of the pubUc analyst in order to assist his interpretation
of the results obtained from the formet sample.
A provision of the Act gives the Minister of Agriculture powers
to estabhsh certain minimum limits of composition of milk and
separated milk which shall form the basis upon which a presumption of adulteration may be raised. These are contained in the
"Sale of Milk Regulations, 1939," and are to the effect that if a
sample of milk (other than separated milk or condensed milk) is
found to contain less than 3 per cent of fat or 8-5 per cent nonfatty solids, it shall be presumed, until the contrary is proved,
that the milk is not genuine by reason of abstraction of fat or
non-fatty solids, or by the addition of water. A similar clause
relating to separated milk fixes the minimum Hmit of composition
as 8-7 per cent non-fatty solids.
So much contention has arisen over this particular section of
the Act t h a t some more detailed examination is necessary. I t is
apparent that the limits 3 per cent fat and 8-5 per cent non-fatty
solids are well below the average for normal milk and there are
some who would argue that on this accoimt the production of
low quality milk is encouraged. Others there are who contend
that as genuine milk is known on occasion to' fall below these
limits, there may be many unjust convictions. The former
argument is countered by the latter since any increases in the
minima would lead to many more unjust prosecutions. The
latter argument cannot be denied but any further lowering
of the minima would not be in the public interest. The figures
therefore represent a compromise between these two points
of view.
96
97
98
years a great mass of evidence has established this fact, and the
equally important one that abnormal milks of low non-fatty solid
content possess normal freezing-points. If, however, the low
percentage of S.n.F. is due to watering the freezing-point will be
higher than normal, i.e. the freezing-point depression will be less.
Actual observations indicate a slight tendency for abnormal milks
to show lower freezing-points (greater freezing-point depressions)
than normal. I t is necessary to point out that to obtain the true
freezing-point a number of corrections have to be apphed to the
observed reading, but when the results are required for comparative purposes only, these corrections may be omitted provided
the apparatus and technique are standardised. The commonly
used apparatus and technique are those of Hortvet, and it is
customary to record the freezing-point asC. (Hortvet).
Elsdon and Stubbs^ examined 1,000 samples by this method
with the following results:
FBEEZING-POINT DEPRESSION C.
No. of samples
Minimum .
Maximum.
Average .
A.M.
P.M.
Unknown
Total
440
0-530
0-563
0-545
500
0-529
0-563
0-544
60
0-530
0-556
0-544
1000
0-529
0-563
0-544
99
parts and the freezing-point depressions, as found by six independent analysts, were: 0-549, 0-550, 0-552, 0-549, 0-551, 0-549.1
AschafEenburg and Temple ^ found no evidence t h a t the stage of
lactation has any influence on the freezing-point of milk, but a
very slight but definite decrease in the freezing-point depression
was noticed at the time of year when spring pastures became
available to the animals. This effect was found to persist for
several weeks.
Andrew^ records an instance of the mixed milk of a herd
containing 4-2 per cent fat and 8-2 per cent non-fatty solids.
Although a presumption of added water would be raised on this
analysis, the freezing-point as determined by a somewhat different
method proved to be normal, namely, 0-55C. Four of the cows
were found to be suffering from mastitis and their milk gave the
following analj^ical data:
Cow 6
% rat
. .
% S.n.F.
Freezing-point
4-00
7-80
-0-555C.
Cow 8
2-40
5-76
-0-550C
Cow 10
4-00
7-64
-0-560O.
Cow 13
3-70
8-00
-0-560C.
100
101
attention, as a result of whicli, it is found that although pasteurisation and sterilisation are not entirely without effect, they are
unlikely to interfere with the normal interpretation of the results
of the test.
It is not proposed to deal with practical details in this section, but
the author wishes to make it clear that the determination is not one
to be entrusted to an assistant who has not received thorough training
in all its technicalities, and whose skill in operating the test has %of
been thoroughly checked from time to time.
The Nitrate Test Sor Added Water.Since natural water
supplies often contain nitrates, whereas milk contains no appreciable traces, it is clear that the presence of nitrates in milk may
be taken as evidence of watering. The test has many hmitations,
for example, their absence cannot be taken as a criterion of
genuineness because some pubUc water supplies are free from
nitrates. Another limitation lies in the fact t h a t nitrates in milk
are slowly reduced and, as a consequence, an acid sample which
originally would have given a positive result may escape detection.
Vieth's Ratio.This, like the nitrate test, is valuable in furnishing confirmatory evidence to the freezing-point test and other
analj^ieal data. Vieth found that the ratio of percentages lactose:
protein: ash for normal milk is 13 : 9 : 2. Abnormal milk, i.e.
genuine milk low in percentage S.n.F., has a different ratio
owing to the lower lactose'and higher chloride content. Watering
a normal milk dilutes each of these constituents to the same extent,
and there is thus no alteration in this ratio. If a sample of low
non-fatty solid content is found to have a normal Vieth ratio a
very strong presumption of added water is raised and valuable
evidence is supplied to support that of the freezing-point test.
Refractive Index oi Milk Serum.By the addition of a prescribed copper sulphate solution to milk, the colloidal matter is
precipitated and on filtering a clear serum is obtained which may
be examined with a dipping refractometer. From the reading of
the instrument, the refractive index of the serum may be calculated if desired, but in most cases the reading alone suffices. The
average reading at 20C. is approximately 38, and in the opinion
of some workers a reading less than 36 would indicate added
water. As the value is known to be at least as variable as the
percentage S.n.F., it cannot be relied upon to detect added water,
and must therefore be regarded as a confirmatory test. I t suffers
from the same effects of acidity as does the freezing-point test,
102
becaiise the refractive index increases with increasing concentration of the serum. The most serious hmitation hes in its
inabiUty to discriminate between watered milk and abnormal
samples.
Regarding other forms of adulteration, it is impossible at
present to detect addition of separated milk or removal of fat,
so that reliance must be placed on the estimation of fat, which,
if below 3 per cent, raises a presumption of adulteration. ,
CHAPTER IV
T H E E F F E C T S O F H E A T ON M I L K A N D T H E
A C T I O N O F M I L K ON M E T A L S .
DAIRY DETERGENTS.
CHLORINE
STERILISATION
I N an earlier chapter reference has been made to the changes
brought about by heat on the various milk constituents, but it
is convenient to regroup and supplement these observations under
one heading.
The effects of heat on milk depend upon three factorstemperature, time of holding, a n d p H . The first two are very closely
related, as may be seen from the following figures relating to the
heat coagulation of milk: ^
Temperature C.
Time in minutes for
coagulation to.occur
131
128
123
116
114-5
10
12
20
45
60
'
-0-25
0-35
180
150
0-40
0-50
0-57
60-65
104
105
4-23
3-75
4-06
3-56
0-77
3-06
0-76
3-30
The authors point out that it cannot be assumed that the loss of
creaming properties is directly related to changes involving bound
water.
I n addition to the 'caramelising' effect on lactose, it has been
observed t h a t when milk is maintained near boiling-point there
occurs a further decomposition of this compound. The acidity
of milk which, on first heating, shows a slight decrease due to
expulsion of carbon dioxide, increases at the rate of about 0-09 per
cent (calculated as lactic acid) per hour when milk is kept near the
boihng-point. Under these circumstances lactose decomposes into a
number of acids, amongst which formic acid has been identified.^
.
106
Treatment
Raw milk
Heated milk30 mins. at
,
>
,
,
,
,
,
,
,
J
J
J
?
J
57-5C.
60C.
61-5C.
63C.
65C.
67-5C.
70C.
74-8C.
80C.
.
.
.
.
.
.
.
Depth of cream
layer*
mm.
% of total
albumin and
globulin denatured
12-3
14-0
15-3
13-3
105
5-3
2-5
2-0
2-0
2-3
2-7
5-5
7-4
11-0
15-6
20-5
33-4
82-0
99-1
107
108
109
experiments that known as the Lanarkshire experiment is noteworthy. The growth response of school-children of both sexes
between the ages of five and twelve was carefully recorded for
groups receiving daily supplements of three-quarters of a pint of
milk. The experiment involved 20,000 children living in densely
populated areas. All children receiving milk supplements showed
marked improvement, but the authors further stated: "In so far
as the conditions of this investigation are concerned, the effects
of raw and pasteurised milk on growth in height and weight are
so far as we can judge equal." This experiment has been the
subject of much criticism. The same figures were taken by Fisher
and Bartlett,! who, after regrouping them, concluded t h a t the
experiment showed a definite superiority of raw over pasteurised
milk. The author has no wish to reopen the controversy, but
rather to state t h a t this experiment and the various contradictory
conclusions drawn therefrom illustrate the present situation very
clearly. Not only do different experiments lead to different conclusions, but sometimes the results of any one experiment may be
interpreted in either direction. I t is impossible from the evidence
at present available to state whether or not pasteurisation is likely
to affect the nutritive value of milk. The author's own opinion is
t h a t so far as the normal human diet is concerned the nutritive
value of milk is not significantly lowered by pasteurisation.
Milk and Metals.^Modern methods of storage, distribution, or
processing result in the contact of milk with metallic surfaces for
varying lengths of time, and it is therefore a matter of great
importance to ascertain whether milk has any deleterious effect
on the metal and vice versa. Further, as these metalHc surfaces
must be regularly and thoroughly cleaned and sterilised, it is
equally important to know whether the metal is able to resist
the wear and tear of abrasion and the attack of detergents
used in these operations. I t must be realised also that in the
selection of a suitable metal for any particular part of dairy
equipment, considerations such as mechanical strength, specific
heat, and conductivity may take precedence over all others.
The Action of Milk on Metals.^Metals in contact with solutions
of metallic salts will undergo a certain amount of corrosion
depending on the solubiHty of the metal in the particular solution.
Normally a point of saturation is reached beyond which no more
metal dissolves, but in the presence of proteins this equilibrium
> Fisher and Bartlett, 1931, Nature, April 18.
no
145F
boiling-point
.
.
.
.
1 hour at 140F. bright surface.
6-00
14-15
4-45
6-45
19-90
5-45
25-16
' Hunziker, Cordes, and Nissen, 1929, /. Dairy Sci., 12, 140, 252.
2 Rice and Mi.scall, 1923, J. Dairy Sci., 6, 261.
111
112
DAIRY DETERGENTS
113
114
DAIRY DETERGENTS
115
Concentration of Solution
0-5%
Sodium hydroxide
Sodium carbonate
Tri-sodium phosphate crystals .
Borax crystals
Sodium sequicarbonate, Na2C03
NaHCOs 2H2O
20
more t h a n 60
1-5%
10
60
45
more than 60
2-0%
3%
4-8
more t h a n 24
less than 2
more than 24
>
Jf
if
t9
99
116
DAIRY DETERGENTS
117
118
CHLORINE STERILISATION
119
120
CHLORINE STERILISATION
121
equally satisfactory. At room temperature in closed vessels
exposed to artificial or diffused dayKght, the hypochlorite
solutions were affected more than chloramine T.
If chlorine sterilisation is to become more common there
will be an urgent necessity to warn dairymen that no trace of
the steriliser must be allowed to pass into the milk. Under the
Foods and Drugs Act this would constitute a serious offence.
The detection in milk of traces of hypochlorite solutions is rendered possible by the fact that in those cases where the product
does not normally contain chlorates, the manufacturers have
agreed to include traces, which may be detected in milk by the
method of Wright and Anderson, Analyst, 1938, 63, 252.
The strength of a chlorinating solution may be determined by
addition of potassium iodide and acetic acid to a measured volume
of the solution. A quantity of iodine equivalent to the available
chlorine is liberated and may be titrated in the customary way
with standard sodium thiosulphate solution.
CHAPTER V
CREAM,
BUTTER,
AND
MARGARINE
% Water
%Fat
% Lactose
% Protein
%A8h
Thick cream
Thin cream
39-37
56-09
2-29
1-57
0-38
63-94
29-29
3-47
2-76
0-54
123
under the Sale of Foods and Drugs Act. Preservatives are also
prohibited.
Conditions affecting the Rising of Cream.Fat globules being
of lower density than the Hquid in which they are suspended will
tend to rise to the surface, just as a stone dropped into water
will sink to the bottom on account of its greater density. The
same force of gravity operates in both cases, but the ascent of fat
globules is opposed by a number of factors which do not possess
the same significance in the parallel exaipple of the stone falKng
through water. Friction on the sttrface of the globule will retard
its upward motion, and this opposing force depends upon two
factors, the viscosity of the liquid through which it moves and
the surface area of the globule. The thicker (more viscous) liquids
wiU cause a much greater retarding action than the more mobile
ones. Because small globules possess a much larger surface area
per unit weight than larger ones, the former will rise much more
slowly than the latter. These observations are collected together in the form of a well-estabUshed mechanical formula
known as Stokes' equation
2rnds-df)g
9n
where V =
r =
da =
df =
g =
n =
124
126
126
127
128
129
Per cent
Fat
Water .
Protein .
Lactose.
Ash
.
.
.
.
.
63-00
29-50
4-03
2-80
0-67
Fat .
.
Milk S.n.F.
Sugar
Gelatin
Total solids
Water
Freezing-point
' .
General range
Composition of a
typical ice-cream
mix
Per cent
Per cent
8-18
6-12
13-17
0-25-0-50
30-40
70-60
12
10
14
0-3
36-3
63-7
-2-26C.
130
Milk .
.
,
.
Cream
Separated milk powder .
Pat
S.n.F.
Per cent
Per cent
3-5
50
8-75
4-5
96-5
131
a + b + o = 85-5
Equation 1
a lbs. of cream will give 0-5a lbs. of fat.
c lbs. of milk will give 0-035c lbs. of fat.
therefore, as the mix must contain 10 per cent fat we have,
0-5a+0-035c = 10
Equation 2
a lbs. of cream will give 0-045a lbs. of milk S.n.P.
b lbs. of separated powder will give 0-965b lbs. of milk S.n.F.
c lbs. of milk will give 0-0875c lbs. of milk S.n.F.
As the mix must contain 10 per cent of milk S.n.F., it follows
that
0-045a+0-965b+0-0875c = 10
.
.
.
.
Equation 3
From equation 2
0-5a = 10-0-035c
a=20-0-07c
Substituting for a in equation 1 we have:
(20-0-07o)+h+0=85-5
b+0-93c = 65-5
.
.
Substituting for a in equation 3:
0-045 (20-0-07c)+0-965b+0-08750 = 10
0-9-0-00315C+0-965b+0-0875C = 10
0-965b+0-08435c = 9-l
.
multiply equation 4 by 0-965:
0-965b+0-89745c = 63-208
subtract equation 5 we have:
0.-8131c=54-108
c = 66-54
From equation 2 a = 2 0 - 0 - 0 7 c
= 20-4-658
= 15-342
From equation 1 b = 8 5 - 5 - ( a + c )
= 85-5-81-88
= 3-62
The mix is therefore made up as follows:
Cream
.
.
.
.
15-34
Separated milk powder
.
3-62
Milk
66-54
Sugar
.
.
.
.
14-00
Gelatin
.
.
.
.
0-60
Equation 4
Equations
lbs.
lbs.
lbs.
lbs.
lbs.
100-00 lbs.
132
Milk S.n.F.
133
134
135
Butyleneglycol
Concentration of
diacetyl in butter
Parts per million
0 -0-3
0-5-1-5
1-0-3-0
3-0-5-0
0-1 -0-15"
0-15-0-25 as lactic
0-25-0'40
acid
0-40-0'75
Per cent
Flavoiu'less .
Mild
Medium
EuU .
136
0C.
72
120hours.
The butter was in a state of advanced rancidity in one week.
With 2 p.p.m. of copper the fishy taint appeared in 48 hours and
the taUowy taint in 72 hours. Contamination with 10 p.p.m. of
copper caused the tallowy taint to appear so quickly t h a t no
fishiness could be detected. Acidity in all cases hastened these
changes. As shown in the table; the effects of Nickel, Manganese,
Chromium, and Iron were not so severe as those of copper, but
here again they were hastened by acidity. I n addition to its effect
on flavour, fat oxidation is known to cause losses of vitamin A.*
1 Prill and Hammer, 1939, J . Dairy Sci., 22, 67.
2 W. L. Davies, 1937, Proc. Uth World's Dairy Congress, Berlin, 2, 124.
=> Hilditch, 1944, Chem. and Ind. p. 67.
137
Fishy
Tallowy
5
10
25
5
4
3
9
8
7
138
139
Every 100 lbs. of cream must lose 0-550-15 =0-40 lb. of lactic
acid. If sodium bicarbonate is to be used it will be necessary to
use 0-4X 0-93 =0-372 lbs (approximately 6 ozs.), if neutralised
with anhydrous sodium carbonate 0-4 x 0 ' 5 9 = 0 ' 2 3 6 lb. (3-75 ozs.)
would be required, or 0-4 x 1-69 =0-636 lb. (approximately 10 ozs.)
of sodium carbonate crystals NagCOs 10 HgO.
Carbon dioxide gas being slightly soluble, the full reduction of
hydrogen ion concentration will not be effected until pasteurisation
removes some of this gas. Hunziker^ suggests t h a t the required
amounts of sodium carbonate (anhydrous) or sodium bicarbonate should be weighed and dissolved in water to make a 10 per
cent solution which is sprinkled on the surface of the cream with
constant agitation. There is a tendency for highly acid creams to
froth when the bicarbonate is used, but this may be overcome by
dissolving in hot water and adding the solution hot. Some
authors^ consider it desirable to warm the cream to 80-90F., and
to add the neutrahsing solution to the warm cream.
Over neutrahsation may cause difficult churning and may
produce a soapy butter of poor texture and unsatisfactory
keeping qualities. Neutralisation must therefore be carried out
with the utmost care, and its success will largely depend upon the
accuracy with which the acidity of the cream is determined.
Even when satisfactorily performed it is admitted that butter
made from neutrahsed cream does not possess the keeping quahties
of ripened sweet cream butter. One reason is t h a t although the
process may neutralise the bulk of water soluble lactic acid, it does
not effect a proportionate reduction in the fat soluble acid.
The influence of salt on the keeping quality of butter is a matter
of interest for while salt is antagonistic to most bacteria and moulds,
the common experience has been that butters containing over
2 per cent of salt do not keep so well as shghtly salted ones. One
possible explanation for this may be the increased solubility of
lecithin in salt solutions whereby more of this compound enters
the aqueous phase, where acidity and dissolved oxygen favour
its oxidation.
Badly flavoured butter may occasionally be rendered edible
by melting, and washing the fat with warm water in order to
remove the products of decomposition as far as possible. The
fat may then be emulsified into milk or separated milk. This
' Hunziker, 1927, TU Butter Industry, p. 168.
" Totman, McKay, and Larsen, 1939, Butter, p. 122.
140
Hunziker^
86-85
11-54
81-5
15-0
83-5
15-2
0-59
1-02
1-0
2-5
1-3
0-0
Ling*
Cox'
86-82 84-94
12-15 14-26
81-97
15-03
82-22
11-74
81-79
14-00
88-6
12-5
0-75
0-05
0-70
2-30
1-01
5-03
1-31
2-90
0-7
0-2
1-00
0-03
141
At the time of writing margarine enters largely into our wartime diet and, in the author's opinion, an excellent standard has
been maintained in spite of limitations of supply. The second
great war has seen margarine come into its rightful place. The
modem product rehes mostly on vegetable oil seeds as sources
of fat and upon ripened separated milk as a flavouring agent.
Ground nuts (monkey nuts), coco-nuts or copra, palm kernels, and
soya beans are all able to furnish oils which are used in making
margarine. These oils are extracted from the seed and the residues
provide valuable oil cakes or meals for stock-feeding. The oils
are decolorised, deodorised, and purified to such an extent as
to be practically without taste. They are then blended to give a
mixture having the same melting and setting ranges as butter
fat. Climatic conditions are also considered in the blending
process. Oils from the soya bean and ground nut are liquid, but
they may be rendered solid or semi-solid by the fat hardening
(hydrogenation) process:
unsaturated liquid fat-|-hydrogen= more saturated semi-sohd fat.
Liquid ground nut oil, for instance, may be hardened by this
process to give a fat melting at 35C., or even higher if required.
This highly technical process has placed a much wider range of
oils at the disposal of the margarine manufacturer: a matter of
great importance in time of war.
The successful making of margarine also depends upon the
development of butter flavours in pasteurised separated milk by
inoculation with butter cultures, which are generally propagated
in the bacteriological laboratories attached to the works.
The oils are homogenised into the ripened separated milk in
the proportion of 80 per cent oil to 20 per cent separated milk.
The temperature of emulsification varies between 25-40C.,
according to circumstances. Concentrated preparations of
vitamins A and D are added at this stage. The emulsion flows on
to the surface of a revolving drum which is cooled internally to a
temperature of 15C. An exceedingly thin film of frozen
emulsion is removed from the drum by a scraper and conveyed
to a maturing room where it is left some hours at ordinary
temperature. During this time the fat absorbs the flavours
produced in the ripened separated milk and its physical condition
slowly adjusts itself to the new temperature. I t is then worked
like butter, again allowed to mature and then thoroughly mixed
142
MABGABINB
Possesses similar physical structure but is produced by emulsification of vegetable oils in ripened
separated mUk.
143
CHAPTER VI
145
146
147
Preliminary experiments by Berridge have shown t h a t at temperatures above the critical 10-20C. range, the temperature
coefficient is 1-3 to 1-6 per degree Centigrade. The only relevant
reaction showing a similar temperature effect is t h a t of protein
denaturation. The hypothesis is advanced t h a t stage 2 of rennin
action is a process of protein denaturation, t h a t is a regrouping
of poly-peptide linkages within the protein complex, and it gains
support from the well-known fact that increases in concentration
of calcium ions cause marked acceleration of the formation of a
clot. There are parallel instances of protein denaturation being
stimulated by calcium ions. Very small additions of calcium
N
equivalent to
in milk, were found by Berridge to have such
^
6000
a pronounced hastening effect on this stage t h a t he came to the
conclusion t h a t the concentration of calcium ions normally
present must be of a very low order.
Hankinson and Palmer^ studied the action of rennin on calcium
caseinate systems and came to the conclusion t h a t the enzyme
renders the casein unstable by virtue of a process of dehydration.
The change which occurs when rennin attacks milk may be
written as:
CagPjOg [calcium caseinate I
148
149
23
28
33
38
43
48
Time of coagulation in
minutes .
36
IM
7-5
6-5
.6-0
6-6
The retarding effect at 48C. was probably due to the commencement of heat inactivation of the enzyme.
Effect of Acidity.Small increases of acidity hasten rennet
coagulation, and it is probable t h a t both stages are stimulated by *
this factor. Alkahnity is unfavourable to rennet activity. T h e '
general effects of small increases of acidity are to be seen from the
following figures of Davis.^
Lactic acid increase
Time of coagulation
0%
0-01%
0-025%
0-05%
22-5
12-0
5-25
2-33
,
pH of the sample .
5-7
6-08
6-52
6-98
7-53
29
48
196
1186
no
coag.
151
Time of coagulation
in minutes
1-6-1-8
1-8-2-0
2-0-2-2
2-2-2-4 ^
2-4-2-6
2-6-2-8
2-8-3-0
3-0-3-2
3-2-3-4
% Soluble
CaO
% Soluble
inorganic
0-059
0-058
0-062
0-063
0-059
0-064
.
0-068
0-089
0-089
0-085
0-084
0-086
0-084
0-081
Eatio of sol.
Calculated %
inorganic
soluble calcium .
P2O5 to sol.
citrate.
CaO
Expressed as CaO
1-606
1-657
1-414
1-340
1-446
1-320
1-206
0-028
0-032
0-037
0-038
0-035
0-039
0-056
Sample
Age in hours
Time of coag. in minutes
Sample
Age in hours
Time of coag. in minutes
12 3
5
27 3
10
3 27
4-3 5-0 3-4 3-7 2-8 3-1 1-9 2-4
E
10 27 4
3 "27
3
10 28
2-1 2-4 2-4 2-5 2-8 2-9 3-3 \ 3-6
i
153
154
155
156
provide useful guidance throughout the operations of cheesemaking, especially when combined with keen observation of other
characteristics. I t is interesting to note how the control of cheesemaking has been raised from indirect empirical observations
prior to 1899, when Lloyd^ first introduced the acidity tests, to
the present day when rheological measurements are being considered and when serious attention is being given to the desirabihty of using ^ H measurements either instead of or together
with the acidity tests. Hydrogen ion concentration may be determined accurately only by the use of a potentiometer, but it is
extremely doubtful whether the normal cheese factory would be
justified in aiming at this degree of accuracy. I t is by no means
estabhshed as yet t h a t under the guidance of ^ H values rather
than acidity tests, the quality of the finished cheese is improved.
The ^ H may be determined approximately using a colorimetric
method,^ but even this is not so rapid or convenient as the usual
titration value.
Natural acidity has been discussed in Chapter I I when it was seen
that some variation may be expected from cow to cow. When
milk is bulked at a cheesemaking factory it is unlikely t h a t serious
difficulty will arise on this score, but in the making of farmhouse
Cheddar, M. C. Taylor* has observed t h a t when the cheesemaker
follows rigidly the rule of adding rennet at an acidity of 0-22 per
cent, difi&culties arise quite frequently. I n her experience, milk
which started with a low natural acidity should be renneted before
0-22 per cent according to the rate of acid development, while
milks which had a high natural acidity require an acidity greater
than 0-22 per cent before rennet is added. To overcome the disturbing influence of variations in natural acidity in cheesemaking
on a small scale, the rate of acidity development should be the
guide rather than the actual acidity figures. I t has been observed
that milk of high natural acidity shows no quicker coagulation
with rennet than do those of lower values.*
An interesting fact about the protein of the newly made cheese
is its solubility in warm salt solutions 3-10 per cent strength.
I t is considered t h a t apart from other considerations the presence of
salt in cheese is desirable on this account. With a hard cheese of 33
per cent moisture, the salt percentage on this basis alone should lie
1 Llovd, 1899, Report on Cheese Making, H.M. Stationery Office.
2 Davis and Thiel, 1940, J. Dairy Res., 11, 71.
M. C. Taylor, 1929, Agricultural Progress, 6, 80.
Eice and Markley, 1924, J. Dairy Sci., 7, 468,
167
158
AGE OF CHEESE
Temperature
32F. .
55F. .
60F. .
70F. .
1-5 months
3 months
6 months
12-8
20-56
23-14
29-24
18-64
31-46
33-69
40-13
23-06
36-09
39-97
45-50
1-5 months
3 months
6 months
0
1-5
2-5
5-0
23-42
21-80
21-67
18-84
0
0-59
0-82
1-29
34-26
32-10
29-92
27-70
0
0-70
1-20
1-50
40-52
37-67
34-73
31-70
0
0-84
1-15
1-62
159
160
161
Fat
Fat in dry
matter
Wensleydale .
Caerphilly
Lancashire
White Stilton
Gloucestej
Cheshire
Derby .
Leicester
Blue Stilton .
Cheddar
Cream .
S.D.
45-03
44-67
44-28
41-76
41-0
40-53
39-95
39-79
37-64
36-69
24-5
3-72
2-96
1-82
4-13
2-36
1-62
2-61
3-96
2-34
3-56
%
\
27-72
28-43
27-39
32-44
28-8
29-96
30-59'
30-21
35-71
31-82
71-6
/o
S.D.
/o
S.D.
2-62
2-00
1-49
3-53
1-83
1-62
1-43
3-52
1-65
3-49
50-23
51-23
49-10
55-37
49-0
50-30
50-70
60.00
57-20
50-20
2-42
2-36
1-88
3-14
.
2-10
2-12
1-89
3-08
1-98
27-25
26-90
28-33
25-80
30-2
29-51
29-46
30-00
26-65
31-49
3-9
Protein 1
ash and No. of
lactic samples
acid
Cheese
111
234
403
124
3
606
11
24 '
212
363
49
162
Coulommiers
(double cream) .
Camembert
Brie .
Pont I'eveque
Gruyfere
Cheshire
/o
%Water
%Fat
%Protein
Ammonia
57-8
53-8
53-6
51-0
35-7
31-1
25-0
22-0
22-5
23-1
28-0
32-3
13-0
17-1
18-0
17-8
28-9
30-9
0-13
0-23
0-18
0-13
0-05
0-20
^"^^ xioo
total N "
44-4
86-1
58-1
43-9
22-9
30-1
163
164
165
CURD
Total 0-5
It is clear that whey removes a large proportion of lactose and
mineral matter originally present in milk. It will also remove a
very considerable proportion of the water-soluble vitamins, and it
is therefore highly desirable that these losses should be compensated as far as possible by conversion of whey into human feedingstuffs. Normally some 60 per cent of milk calcium and 57 per
cent of milk phosphorus are retained by the cheese. Most of
the mineral losses occur before the whey is run.^ If the whey is
too acid at running, the mineral losses are much more severe, and
the resulting cheese is on this account more acid.^ Mattick^ has
examined the mineral content of various cheeses, some of her
results being as shown in table on p. 166.
The similarity between the hard pressed cheeses is very striking.
Mattick also observes that most of the mineral losses occur up to
1 McDowaU and Dolby, 1935, J. Dairy Res., 6, 218.
2 Dolby, McDowall, and McDowell, 1937, J .'Dairy lies., 8, 74.
Mattick, 1938, J. Dairy Res., 9, 233.
166
Ash%
Ca% .
P% .
Ratio Ca/P .
Ca retained .
P retained .
Cheddar
Cheshire
3-75
0-80
0-51
1-57
65-5%
58-1%
3-59
0-69
0-47
1-47
65-4%
51-2%
Leicester Lancashire
3-86
0-76
0-49
1-55
68-0%
55-0%
3-93
0-66
0-44
1-50
65-8%
60-0%
Stilton
2-82
0-107
0-268
0-41
7-8%
21-98%
CH,
167
168
169
35
40
45
50
slightly
more
than 50
55
40
30
20
no curd
CHAPTER VII
CONDENSED
POWDER
171
31
26
20
172
cream of 30 per cent fat and 6-4 per cent non-fatty solids must.be
added to standardise to the correct ra,tio.
6000 lbs. of milk supply ^r'^L^lt^
^ ^ -^
100
The desired ratio is 1 lb. fat to 2-44 lbs. non-fatty soHds. i.e.
192 lbs. fat to 468-5 lbs. non-fatty solids.
Surplus of non-fatty solids = 534468-5 = 65-5 lbs.
1 lb. of cream contains 0-3 lb. of fat which will balance 0-732 lb.
S.n.F.
1 lb. cream contains 0-064 lb. non-fatty soMds, so t h a t each lb. of
cream is able to balance 0-7320-064=0-668 lbs. non-fatty soUds.
65-5 lbs. of surplus non-fatty soUds are balanced by addition of
= 9 8 lbs. of cream.
0-668
This quantity of cream added to the 6000 lbs. of milk will
standardise to the desired ratio of 1 fat to 2-44 of non-fatty solids.
A similar calculation is used to calculate the quantity of separated
milk required to balance an excess of fat.
Standardisation is therefore a necessary preliminary to condensation of whole milk, whether sweetened or unsweetened, but
.thereafter the manufacturing processes are different.
Sweetened Coudensed Milk.^After standardisation the milk is
forewarmed with the object of reducing the micro-organic population. I t further assists the solution of sugar which is subsequently added and enables boiling to take place before any
scorching can occur at the surface of the heating coils of the
evaporator. Forewarming temperatiwes near boiling-point render
the product more Uable to thickening defects on storing, and
Hunzikeri recommends 75-85C. (167-185?.).
Sugar may be obtained in a very pure condition, but it must be
stored dry in order to avoid contamination with yeasts and moulds
which would ferment the finished product. The quantity of sugar to
be added is limited at the upper extremity by the saturation level
of sugar in water, and at the other extreme by the minimum concentration of sugar which would exert the desired preservative effect.
On the basis of 31 per cent total milk solids about 17 lbs. of sugar
are added per 100 lbs. of milk. The common practice is to dissolve
the measiu-ed quantity in the warm milk after fore-warming.
^ Hunziker, 1935, Condensed Milk and Milk Powder, p. 62.
173
174
175
176
177
Fat
3-6
Lactose 4-7
Protein 3-35
Ash
0-75
35
Water 87-6
by diff. 69-0
100-0
100-0
Analyst, 1932, 57, 630.
9-0% minimum
11-75
8-38
1-87
added sucrose 17 X 2-5
=42-6
26-5
100-0
Fat .
Lactose
Protein
Ash .
Sucrose
Water
'
9-10%
12-74
8-75
1-94
.
.'
.
67-47
100-00
Sweetened
Condensed
Separated Milk
Sweetened
9-60%
13-07
8-41
1-86
41-92
25-14
100-00
0-29%
14-25
9-53
2-31
46-59
27-03
100-00
179
The heat of the cylinder keeps the milk hot before it passes
through the gap to be taken up as a film by each roller.
If the liquid has been pre-condensed, it may be taken up by
the heated roller which dips into it; or a small unheated roller
may dip into the condensed milk, transfering the film to the
heated one which revolves in contact with the smaller. Only by
pre-cqndensing is it possible to obtain a sufficiently thick film by
this method of "pick u p . "
The thickness and uniformity of the film are very important
factors. If too thin, drying is very rapid and overheating is liable
to occur. If too thick, the drying may not be complete. Uniformity of thickness is also desirable, although difficult to secure.
If the steam pressure is increased, drying is more rapid and the
speed of rotation of the roller must be increased in order to avoid
over-heating. Thus it would seem that increase of steam-pressure
leads to increased output per roller. However, other factors are
involved, and this relationship holds good only within a restricted
range. A short period of heating is essential if the solubility of the
powder is not to suffer severe losses. The whole process may be
carried out at atmospheric pressure under a hood to remove the
steam, or the drying may take place at a much lower temperature
under reduced pressure.
The precise combination of these variants depends very much
upon the material to be dried, the purpose for which the dried
product is intended, etc. I n one of the double roller machines
the rollers measure 10 ft. long by 3 ft. diameter, and they make
no more than 16 revolutions per minute, the steam pressure
varying from 48 to 80 lbs. per square inch.
The spray or atomiser drying process depends upon converting
the liquid into an exceedingly fine mist in which the droplets are
about 0-002 inch in diameter, and which are caused to evaporate
spontaneously by contact with a current of hot air. There are
various methods of obtaining the spray. The liquid may be
forced at 2,000 to 3,000 lbs. pressure through nozzles which may be
stationary or rotary. Another method is to aUow the hquid to
fall on a rapidly revolving disc which flings it away by centrifugal force as a fine spray. The principle of the scent spray is also
used in which a jet of the liquid meets a powerful blast of compressed air. Pre-condensing is usual, one reason being that heat
is used more efficiently in the vacuum condenser t h a n in the
spray chamber. The hot air may be between 100 and 150C.,
12*
180
181
Whole milk
Separated mUk
Cream
Buttermilk
Whey
Malted milk .
Water
Fat
2-5
2-5
0-7
7-0
4-0
3-0
27-5
1-0
65-0
6-5
5-0
8-0
26-5
38-0
13-4
36-5
12-0
18-0
0/
0/
/o
/o
37-5
50-5
17-9
35-5
70-0
12-0
6-0
6-0
8-0
3-0
8-5
9-0
3-8
55-0
.
'
0-2
Elsdon and Walker^ quote figures for the analysis of dried milk
to which sucrose has been added, the concentration in the dried
product being approximately 2 per cent.
182
^183
CHAPTER
DAIRY
Vin
T H E chief dairy by-products, whey, separated milk, and buttermilk, are valuable foods, but their perishable nature necessitates
rapid utilisation; or, if this is not possible, they must be condensed,
dried, or otherwise treated. Their virtues as animal feeding-stuffs
are well established and in the liquid form large quantities are
utilised in this manner. There are, however, serious limitations
to this procedure. When butter and cheese were more generally
farmhouse products, these by-products were produced under
circumstances which enabled their immediate local utilisation,
but with the advent of the creamery and cheese factory large
surplus quantities of the by-products accumulated. Under these
conditions there is a tendency to regard them as perishable goods
to be disposed of rather than valuable foods to be utilised to fullest
advantage. Further, it is the conviction of many that these
by-products are utilised to the full only when used for human
nutrition. We are reminded of whey by Samuel Pepygi in his
own inimitable style: "June 10, 1663. Thence to the whey house
and drank a great deal of whey, and so by water home." I t is
certainly significant t h a t in those days of large and unrestrained
appetites, there was a place for Uquid whey in the diet of such
a joyous gourmand as Pepys. The ancients were familiar with
its medicinal properties, for Hippocrates prescribed whey for the
cure of scurvy, intestinal and even mental disorders. There is no
doubt of the historical popularity of whey. These considerations
give cause for some anxiety over the present-day neglect of this
commodity as a human food.
The table on page 185 gives the composition of typical samples
of these by-products which, naturally, show some variation.
Utilisation of the three by-products in their complete forms as
feeding-stuffs may be effected in the raw, condensed, or dried
conditions. Condensation and drying, besides rendering them less
perishable, reduce transport costs. They have been used very
successfully in the baking and confectionery industries. When
^ The Diary of Samuel Pepys, entry for June 10, 1663.
184
DAIRY BY-PRODUCTS
185
BiTTTBEMILK
Whey
Water
FatLactose
Lactic acid .
Protein
Ash
Vitamins
.
.
.
.
Separated Milk
Buttermilk
90-6
90-8
93-4
0-3
0-1
0-5
4-8
4-9
3-9
undeterundetermined
mined
0-6
0-9
3-6
3-6
0-6
0-8
0-7
All water soluble vitamins of milk
present
Fat soluble vitamins negligible
186
DAIRY BY-PRODUCTS
187
the farmhouse or buildings, etc., in order to eliminate the possibilities of sewage contamination. If the water supply is known
to be contaminated every effort should be made to discover and
ehminate the source of the trouble, but in the meantime, it may
be necessary to utilise chlorination. This step should be taken
only on the advice of a bacteriologist quahfied to deal with such
matters. Prequent checking of the efficiency of the measures
taken would be necessary.
From a chemical point of view the most practical consideration
is the hardness of the water supply. Boiler scale, or scale formation in bottle-washing machines are the result of hardness in the
water used for these purposes. Calcium bicarbonate dissolved in
water is precipitated as calcium carbonate when the water is
boiled, or with an alkah detergent a film of calcium carbonate
settles on the parts of washing machines which are in contact
with the detergent. The chemical changes are represented by the
equations
boil
188
boiler. The problem does not lend itself to hard and fast recommendations. Much depends on the degree of hardness of the
water supply and the steam requirements of the dairy.
Common methods of water softening are the Ume-soda process
and the zeohte or base exchange system. I n the former, the
calculated quantities of hydrated hme (CaOH)2 and 'Sodium carbonate NagCOg are added in order to precipitate the compounds
responsible for temporary and permanent hardness. The zeolite
process involves the percolation of water through a vessel containing the zeoMte whereupon a process of base exchange is brought
about, calcium and magnesium leaving the water to enter the
zeohte and their places being taken by sodium.
Na-zeolite -j- Ca-water = Ca-zeolite -f- Na-water
By this method both types of hardness are removed, and the
process is self-regulating. The zeolite may be recharged by running
a solution of salt through the apparatus.
Ca-zeolite -f NaCl = Na-zeolite -f- Calcium chloride
For convenience, the zeolite process has much to commend it.
Salt for Dairy Purposes.Salt is obtained in this country from
several natural salt deposits in Cheshire and Worcestershire. The
brines from which the salt is crystallised may contain some 25 per
cent sodium chloride, 0-2 per cent magnesium chloride, 0-4 per
cent calcium sulphate, and a trace of calcium bicarbonate. The
operations of brine purification, evaporation, and crystalhsation
have as their object the ehmination of these impurities from the
salt. Calcium sulphate being only slightly soluble may impart
a gritty texture to the salted dairy product while magnesium
chloride, being intensely hygroscopic, tends to make the salt damp.
Contrary to the general behef in the germicidal properties of salt,
it is known t h a t damp salt may introduce various micro-organisms
into dairy products. Only by keeping salt dry is it possible to
avoid such contamination. As it leaves the factory, salt is usually
in a very pmre condition, but when allowed to become moist in
the dairy or when stored in sacks which have been used for other
purposes, contamination is likely to occ\ir. For dairy purposes,
it is also desirable t h a t the salt should be readily soluble, and
ease of solution depends upon its fineness. I t is desirable that
the salt should pass a 10-mesh sieve completely and t h a t 90 per
cent of it should pass through an 18-mesh.
DAIRY BY-PRODUCTS
189
190
SEPARATED MILK
BUTTERMILK
BNTIRB
EXTRACTED
I
Add Dilute Acid
Used for Human
and Animal Nutrition
Baking and
|
Confectionery
Whey
m
Natural, Condensed,
or
Dried Forms
Add Rennet
|
|
|
Acid Casein Rennet Casein Whey
For Plastics, Glues,
Cements, Paints,
Medicinal Products,
Patent Foods, etc.
or Human
Animal
itrition,
s:ing and
ectionery
in
I
EXTBACTED
Nteutralise
Condense
Heat
Decaiit
Heat
Crystalise
Heat
Decant
to
Decant
Crude
Lactc'se
Mother
Liquor
Albumin
Liquid
Condense
Crystalise
Condense
Whev
Mix
with
Dry
Albumin
Animal ^^
Mother
Liquor
Fermentatii
Crude
Lactose
Albumin
'Spread'
Liquid
to
Pigs
Residue
Homogenised
to give
'Whey Milk'
Lactic Aci
Butyric Ac;
Alcohol
Acetic Aci(
NAME INDEX
ANDERSON, 121
Andrew, 99
Arup, 13
Aschaffenberg, 99
Azarme, 84
BABCOCK, 120
Baker, 71, 85
Banxhart, 22
Bamicoat, 164, 166
Bartlett, 74, 82, 89, 109
Benton, 105
Berridge, 146
Binney, 174
Boden, 63
Bosworth, 34, 44
British Standards Institution, 63, 189
Brown. 20
BushiU, 182
FELTHAM, 129
Fenger, 148
Ferguson, 28, 48
Fisher, 109
Folley, 90
Fonts, 14, 137
Frayer, 65
GAINES, 81
Gamett, 81, 82
Gillam, 28, 30
Golding, 71, 80, 86, 15a 159
Gortner, 5, 25, 27, 55
Gould, 20, 37
Graham, 22, 108
Grant, 120
Griffiths, 69, 71, 72, 73
HALLER, 120
Hallett. 146
GMIPBELL, 63, 79
Hammer, 136
Carrie, 167
Hand, 30, 41
Caulfield, 57
Hankinson, 145, 147
Cherbnliez, 37
Hairis, 46, 52
Ckjgen, 1
Harrison, 160
Combs, 86
Haxt, 176
Corbett, 20
Heilbron, 28
Cordes, 110
Heinemann, 22
Corran, 41
Henderson, 60, 78, 80, 111, 112, 127
Cox, 140, 178
Cranfield, 69, 71, 72, 73, 75, 85, 86, 93 Hening, 127
Herrington, 15
Crighton, 44
Hilditoh, 9, 13, 16, 18, 23, 88, 183
Crowther, 71
HiU, 167
,
Crniokshank, 79
Hinks, 90
Hiscox, 160, 161
DAHLBERG, 104, 127, 166
Hohn, 21, 22, 103
Dahle, 18, 63, 105
Davies, 16, 23, 24, 42, 60, 61, 66, 71, Holter, 146
Houdet, 162
72, 78, 79, 135, 136, 137, 149, 164
Houston, 50
Davis, 145, 160, 152, 154, 156, 161
Hoy, 119
Deysher, 21, 22, 103
Doan, 104, 124, 169
Hunziker, 110, 111, 112, 113, 139, 140,
Dolby, 166
172, 173, 175, 176, 181
Dom, 166
Drakeley, 78, 82
IMPERIAL Chemical Industries. 114
ECKLES, 86
JEANNERAT, 37
EUis, 16
Jensen, 40, 104, 105, 126
Elsdon, 61, 67, 71, 72, 76, 78, 81, 85 Ijohns, 160
86, 88, 96, 98, 99, 100, 181
'Johnson, 174
Evans, 100, 103, 174
Josephson, 104
191
192
McKay, 139
McKee, 37
Mellander, 37
Melville, 146
Miscall, 110
Moir, lOd, 153
NEAVB, 119
Nelson, 18
NichoUs, 162
Nissen, 110
Noll, 52, 55
OLSON, 20
Overman, 78, 81, 82, 89
PALMER, 9, 18, 145, 147
Pepys, 184
Perlman, 22
Petersen, 90
PoweU, 88
Price, 149, 157, 158, 159
PriE, 136
Pyenson, 63, 105
Pyne, 36
RAMDSELL, 174
Recknagel, 62, 63, 64
Regan, 15
Reif, 111
Rewald, 22
Rice, 110, 156
Richardson, 15
Richmond, 61, 62, 71, 72, 85, 122
Riddell, 57
Riddet, 89
Roadhouse, 60, 78, 80, 111, 112, 127
Rodgers, 129
Rohen, 14
Rowland, 31, 72, 90, 92, 106, 107, 16';
SCHWARTZ, 168
Scott-Blair, 154
Sharp, 8, 10, 15, 16, 17, 30, 41, 84, 123
126, 145
Shattock, 93
Shaw, 116
Sleightholme, 88
Smith, 89
Sommex, 14, 18, 146, 163, 174, 176
Soulides, 167
Steinbeck, 111
Stokes, 123
Struble, 84, 145
Stubbs, 67, 86, 98, 99
Supplee, 52, 55, 76, 182
Swanson, 18
TARASSUK, 15
Taylor, 156
Temple, 99
Templeton, 163
Thiel, 156
Tocher, 71, 72, 73, 74, 76
Tracy, 20
Troy, 123
Turner, 80
VAN SLYKE, 34, 44, 71, 72, 149, IST
158, 159
Vernon, 160
Vieth, 78, 101, 140
WALKER, 61, 71, 72, 76, 78, 85, 86
88, 100, 181
Wardlaw, 45
Watson, 28, 48
Whelan, 157
Whittier, 105
Williams, 87
Wolf, 160
Wright, 21, 22, 121
ZEIN EL DINE, 92
SUBJECT INDEX
Calcium, soluble, 44, 45, 108, 147, 150,
ABNORMAL milk, 98, 102
Acetyl methyl carbinol, 6, 135, 136
151, 152, 168
Acid curd cheese, 162
Caramehsation of lactose, 5, 103
Acid, lactic, 5, 6, 7, 35, 36, 37
Caxotene, 27, 28, 29, 30, 48, 49, 82, 86
Acidity, efiect of heat on, 105
Casein, 34-39
on rennet action, 149, 150
acidity, 35, 57, 155
natural, 57, 58, 59, 85, 156
heat coagulation of, 39,107,175,176
test, 35, 57, 58, 59, 155, 156, 174
number, 42, 84, 91, 92, 93
Acids, fatty, 10-14
plastics, 38, 39
Added water, 62, 66, 67, 94-102
rennet coagulation of, 37, 38, 146Adermin, 49
154
Adsorption by fat globules, 8, 9, 125, CephaUn, 21
Cheese, 144^166
126, 128, 132, 133, 134
Adulteration of cheese, 162
flavours of, 160, 161
mineral matter of, 166
milk, 94-102
Age of cow, effect on milk composition, ripening of, 32, 157-161
CUoramine T, 118, 119
82, 89
Chlorides, 43, 44, 60, 81, 84, 92
Agglutinin, 105, 125, 126
'
Chlorine sterilisation, 118,119,120,121
Albumin, 39, 64, 106, 107, 152, 153
Alloys for dairy equipment. 111, 112, Cholesterol, 24-27, 142, 143
Choline, 21, 22, 23
113, 120
.
Churning, 133, 134
Aluminium, 111, 112, 117, 120
Amino acids, 32, 33, 34, 157
Citrates, 43, 44, 46, 57, 107, 108, 136,
Aneurin, 49
151, 163, 176, 177
Clotted cream, 128
Annatto, 27, 164, 166, 167
Clusters of fat globules, 8, 105, 106,
Anti-oxidants, 19, 20, 28
Appeal samples, 74, 95, 96
123, 124, 125, 126, 127, 132, 133
Artificial cream, 128
Coagulation of milk by acids, 6, 7, 3 4 Ascorbic acid, 19, 20, 52, 63, 56, 56,112
37, 103
Ash of milk, 42, 43, 84, 101
heat, 39, 103, 106, 107
Average composition of milk, 68, 69,
rennet, 37, 38, 46, 107,
70, 71, 72, 73
146-156
Colostrum, 50, 81, 82, 83
B E R I - B E R I , 49, 50
Colour of milk, 59, 103
Boiling-point of milk, 66, 170, 173
Composition of colostrum, 81, 83
Bound water, 33, 63, 64, 105
milk, 68-94, 94-102
Breed, effects on t h e composition of
by-products, 185
milk, 8, 30, 76, 77, 78
mineral matter of mUk, 44, 45
British Standards Institution, 189
butter, 140
Buffers, 33, 59, 115, 119
cheese, 161, 162, 166
Butter, 132-140
Xcondensed milk, 177, 178
Buttermilk, 184, 185, 186
cream, 122, 129
Butyric acid, 12, 13, 14, 137
dried milk, 181
By-products, 6, 134, 184, 185, 186
Condensed milk, 170-178
Constituents of milk, 1-56
CALCIFEROL, 25, 26, 27
'*
Contamination, metaUic, 17, 18, 20, 23,
Calcium, 44, 45, 46
caseinate, 35, 36, 37, 39
33, 112, 113, 136, 137, 163, 164,
citrate, 108, 151, 176, 177
182
phosphate, 34, 36, 37, 108, 147, 149, Copper contamination, 17, 18, 20, 23,
153, 176, 177
60, 112, 113, 136. 164, 182
193
194
FAT, 7-20
associated substances, 20-30
composition of, 12-14, 84, 87, 88, 89
globules, 7, 8, 84,104,105, 106, 120128, 132, 133
oxidation, 16-20, 136, 137, 182, 183
percentage in milk, 69-91, 95-97,
102
physical properties of, 9, 10
Patty acids of mUk fat, 10-14
, effect of ration, 87, 88, .
89
Feeding, effect on the composition of
milk, 15, 19, 23, 24, 27, 28, 29, 30,
48, 60, 87-89,
Fermentation alcoholic, 4
lactic, 6-7
Fishy taint in butter, 23, 24, 136, 137
milk, 23, 24
Flavoprotein 9, 41,
Flavour of butter, 134, 137
cheese, 160-161
milk, 4, 5, 6, 59, 60, 103
Freezmg-point of milk, 7, 37, 67, 92,
97-101
Frothing, 65, 139
GALACTOSE, 4, 5
Galvanised iron. 111, 113
Gases in Milk, 66, 56
Globules, fat, 7-10, 84, 104, 106, 106,
120-128, 132, 133
Globulin, 39, 64, 81, 106, 107
Grittiness in ice cream, 4, 130
sweetened condensed milk, 4,
,
173, 176
HARD cheese, 153, 154, 165, 157, 161
water, 116, 187, 188
Hardening of fats, 141
Heat coagulation, 39, 103, 106, 176,
176
effects on milk, 103-109, 161, 152
Homogenisation, 15, 65, 123, 124, 125,
132
Hormones, 90-92
Hortvet freezing-point test, 67, 98-101
Humidity and cheese ripening, 169,
160
Hydrogen ion concentration, 57, 150,
156
peroxide and oxidised taints, 20, 112
Hydroxyl ion concentration, 114, 115
Hypochlorites, 118, 119
INDEX
ICE cream, 129-132
Individuality, effect on the composition
of milk, 76
Intervals between mUking, effect on
the composition of mUk, 78-80, 82
Iodine in milk, 43, 44, 108
value of miUc fat, 18
Irradiated milk, 54
KEPHIR, 4
Ketonic rancidity, 16, 137
LACTALBUMIN, 39, 40, 104, 106, 107
Lactase, 4
Lactation, stage of, effect on milk
composition, 8, 57, 60, 81-84
Lactic acid, 6, 7, 37, 58, 61, 67, 99, 100,
101, 135, 136, 137
Lactic fermentation, 5-7, 37
Lactose, 2-7, 60, 81, 84, 92, 103, 105,
136, 158
Lead contamination, 113, 164
Lecithin, 10, 18, 20-24, 139
Legal considerations of milk composition, 94-102 Linoleio acid, 12, 16
Lipase, 14-16, 25, 137, 161 .
MARGARINE, 49, 54, 140-143
Mastitis, effect on the composition of
milk, 31, 92, 93, 99
Metal foil, 113, 163
Metallic contamination, 9, 17, 18, 20,
23, 33, 112, 113, 136, 137, 163,
164, 182
flavour, 60, 112, 113, 164
corrosion by chlorinators, 120
detergents, 117
milk, 109-112
Milk acidity, 35, 57-59, 85, 105, 149,
150, 153, 154, 155, 156
average composition of, 68-73
boiling-point of, 66, 67
condensed, 170-178
constituents, 1-56
enzymes, 108
fat, 7-30
freezing-point of, 67, 97-101
mineral matter of, 42-^6, 57, 84,
108, 150, 151, 168, 176
nitrogen compounds, 31-42
powder, 178-183
stone, 104, 116
sugar, 2-7, 60, 81, 84, 92, 103, 105,
136, 158
195
196
Thiamin, 49, 50
Thyroxine, 91
Tin and tinned metals. 111, 113, 117,
RANCIDITY, 14-16, 137
120
Reoknagel's phenomenon, 62, 64
Titratable acidity of milk, 35, 57, 58,
% Reconstituted cream, 128
59, 85, 105, 155, 156, 174
Refractive index of milk, 66, 101, 102
Tocopherol, 54, 55
milk fat, 10
Total solids in milk, 61, 62, 63
Rennet, 144, 145
Trimethylamine, 23, 24
coagulation, 107, 146-153
curd, physical nature of, 153-155
UNSWEETENED condensed milk,
Rennin, 144-153, 158
174-178
Riboflavin, 41, 49, 50, 55, 166
Richmond's formula, 61, 62
VACUUM evaporation, 170, 173, 175,
Rickets, 46, 53
185
Ripening of cheese, 157-161
salt, 189
Roller drylAg, 178, 179
^;
Variations in the composition of milk,
73-94
,
SALT balance in milk, 43, 107, 176
Vegetable rennets, 144
Salt, dairy, 188, 189
Vieth's ratio, 101