Chem220 Spectrophotometry
Chem220 Spectrophotometry
Chem220 Spectrophotometry
Tutorial #7
Chapter 18: Fundamentals of Spectrophotometry
Chapter 20: Spectrophotometers
Quiz 6 Answer
Conditional formation constants for metal ion – EDTA titrations are
found from the formula K’f = αY4-Kf, where Kf values are tabulated
for many metal ions at 25oC, and αY4- depends on pH. At pH 9.0,
αY4- is 0.041. What is the minimum value of Kf needed for
quantitative reaction of metal ion with EDTA (99% complete reaction)
at pH 9.0, for a 0.01000 M solution of metal ion titrated with a 0.01000
M solution of EDTA?
Half
E = (hc)/(λ)
h= Planck’s constant
c= speed of light
Double
!
E = hc v
h= Planck’s constant
c= speed of light
! (wavenumber) are directly related to
E (energy) and v
one another
2) Calculate the frequency (Hz), wavenumber (cm-1), and energy
(J/photon and J/[mol of photons]) of visible light with a
wavelength of 562 nm.
• v = frequency
= c/λ= (2.9979 x 108 m/s)/(562 x 10-9 m) = 5.33 x 1014 Hz
! = wavenumber
• v
• E = energy
ε= molar absorptivity
= 6.97 x 10-5 M
(0.267 − 0.019)
ε= A/bc = = 7.87 x 104 M-1 cm-1
(3.15x10 −6 M )(1.000cm)
(0.175 − 0.019)
c= A/εb =
(7.87x10 −4 M −1cm −1 )(1.000cm)
c = 1.98 x 10-6 M
6) Nitrite ion, NO2- , is a preservative for bacon and other foods,
but it is potentially carcinogenic. A spectrophotometric
determination of NO2- includes a number of steps. The following
solutions were analyzed:
Note: Sample C contains colored product from nitrite added, absorbance = 0.977
Now, calculate concentration of colored product with a total volume of 54.0 mL:
c = A/εb
c = 0.0002 M or 0.20 mM
8) The transmittance of a 0.010M solution of a
compound in a 0.100 cm pathlength cell is T=8.23%.
Find the absorbance and the molar absorptivity.
• First convert T into a decimalà 8.23% = 0.0823
-A = log (T)
-A = log (0.0823)
-A = -1.0846
A = 1.08
ε= A/(b)(c)
ε = (1.08)/[(0.10cm)(0.01M)]
ε = 1084.6
ε = 1.08 x 103 M-1 cm-1
9) What is the wavelength, wavenumber and
name of radiation with an energy of 100kJ/
mole?
100 kJ/mole = 100000 J/mole
100000J 1mole −19
x 23
= 1.661x10 J / molecule
mole 6.022x10 molecules
ε = 1.661 x 10-19 J/molecule
hc hc
ε= ⇒λ=
λ ε
(6.626x10 −34 J ⋅ s)(3x108 m / s)
λ= −19 = 0.00000119 m = 1.20 μm
(1.66x10 J / molecule)
λ= 1.19 x 10-6 m
8th edition, Chapter 17, Section 17-2 Example, Page 396
Now calculate wavenumber…
1 1 1
ν! = = =
λ 0.00000119m 0.000119cm
! 3
ν = 8.33x10 cm −1
log T = -A
ε= A/(bc) = (0.266)/(1.0)(1.32x10-3)
= 201.3 M-1cm-1
[C6H6] = (A)/(εb)=(0.070)/(201.3)(5.0)
= 6.95 x 10 -5 M
= 5.4 mg/L
12a) What resolution is required for a diffraction
grating to resolve wavelengths of 512.23 and
512.26 nm?
• Resolution = (λ/Δλ)
= (512.245/(512.26-512.23))
= (512.245/0.03)
=1.7 x 104
Δλ= (λ)/Resolution
= (512.23)/(104)
=0.05nm
12c) Calculate the fourth-order resolution of a
grating that is 8.00 cm long and is ruled at 185
lines/mm.
• Resolution=(λ/Δλ)=nN
• n= diffraction order
• N=number of grooves of the grating that are illuminated
• Resolution = nN
= 1.5 x 104
12d) Find the angular dispersion (ΔΦ) between light rays with
wavelengths of 512.23 and 512.26 nm for first-order diffraction
(n=1) from a grating with 250 lines/mm and Φ=3.0o
Given:
n= 1
Φ=3o
Δλ=(512.26-512.23)=0.03nm=3x10-5um
d= (250 lines/mm)(1mm/1000um) = 0.25 lines/um = 4 um/line
12d continued
Δφ n
=
Δλ d cos φ
Δφ (1) radians o
= 0
= 0.250 = 14.3 / µ m
Δλ (4µ m)cos3 µm
o −5 −4
Δφ = (14.3 / µ m)(3x10 µ m) = 4.3x10 deg rees
13a) The true absorbance of a sample is 1.500, but 0.50% stray
light reaches the detector. Find the apparent transmittance and
apparent absorbance of the sample.
T=10-1.500 = 0.0316
0.0316 + 0.0050
= = 0.0364
1+ 0.0050
• Apparent absorbance = - log(T)
(0.010) + S
= = 0.01002305
1+ S
• True absorbance = 2
P+S (0.010) + (0.0000005)
• Apparent transmittance = =
Po + S 1+ (0.0000005)
= 0.01000049
=-log(0.001000495)
=2.999785
S = stray light
- log (T) = A
T = 0.010233
0.000233 = 0.989767S
S = 0.000235 = 0.024%
16) Find the minimum angle θi for total reflection in the optical
fiber in Figure 20-21 if the index of refraction of the cladding is
1.400 and the index of refraction of the core is (a) 1.600 or (b)
1.800.
• Figure 20-21
1.400
sinθi ≥ à θi ≥ 61.04o
1.600
16b) Index of refraction of the
core is 1.800
ncoresinθi=ncladdingsinθr
For total reflection: sinθr ≥1
ncladding
sinθi≥ (Page 462)
ncore
Given:
ncladding=1.400
ncore=1.800
sinθi ≥
1.400 à θi ≥ 51.06o
1.800
17a) If a diffraction grating has a resolution of 104, is
it possible to distinguish two spectral lines with
wavelengths of 10.00 and 10.01 µm?
• Resolution = λ/Δλ
λ= 1 / ν!
• Solve for Δλ
Δλ= λ/Resolution
• First Order
Resolution = (1)(12,5000) = 12,5000
• Tenth Order
Resolution = (10)(12,500) = 125,000
17d) Find the angular dispersion (ΔΦ, in radians and degrees)
between light rays with wavenumbers of 1000 and 1001 cm-1 for
second-order diffraction (n=2) from a grating with 250 lines/
mm and Φ=30o.
Δφ n
• Dispersion of grating: =
Δλ d cos φ
Δφ 2 radians radians
= = 577 = 0.577
Δλ ( 1mm )cos(30 o ) mm µm
250lines
For this problem, we refer to the rules for addition and subtraction:
e= √(12+12+12+12) = 2
average noise = n
=
1
n n
avgsignal 100
= = 100 n
avgnoise 1 / n
which is √n times greater than the original value of signal/noise
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