State Polytechnic of Malang

Malang
2017

Heat Effect
Thermodynamics Course Chapter 4
Agung Ari Wibowo S.T., M.Sc
 Learning Objective
Chapter 4

Heat
Standard
Capacity & Standard Heat
Laten Heat Heat of Standard
Sensible Integral Enthalpy as Effect in
of Pure Reaction Heat of
Heat Evaluation function of Industrial
Subtance and Combustion
of Sensible Temperature Process
Formation
Heat

Literature Used
J M Smith, H C Van Ness, M M Abbott, “Introduction to Chemical Engineering Thermodynamics 7th”
 Sensible Heat
Chapter 4

What happen when you add heat to the

water ?
Temperature
1 • Temperature rise

Boil Water 2 •Water Start to boil

• Continous Evaporation
3 (phase change to
vapor)
Sensible Heat
Chapter 4

At constan Pressure Process

What is 𝑑𝐻 =
𝜕𝐻
𝑑𝑇 +
𝜕𝐻
𝑑𝑃
𝜕𝑇 𝜕𝑃
Sensible 𝑃

𝑇2
𝑇

Heat ?? 𝑄 = ∆𝐻 = න 𝐶𝑝 𝑑𝑇
𝑇1

Heat which causing

the rise in
temperature to the
certain degree with
no change in phase
and composition
 Heat Capacity
Chapter 4

𝑇2 Each substance have their own A, B, C and D

constant. These constant are listed in Appendiks C
∆𝐻 = න 𝐶𝑝 𝑑𝑇
𝑇1
𝐶𝑃
= 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 + 𝐷𝑇 −2
𝑅

𝑖𝑔 𝑖𝑔
Heat capacity of ideal gas can be written as 𝐶𝑣 and 𝐶𝑝

𝑖𝑔 𝑖𝑔 𝑖𝑔
𝐶𝑣 𝐶𝑝 𝐶𝑝
= −1 = 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 + 𝐷𝑇 −2
𝑅 𝑅 𝑅
 Heat Capacity
Chapter 4

Mixture of gases
What is the heat capacity of
mixture?

𝒊𝒈 𝒊𝒈 𝒊𝒈 𝒊𝒈
𝑪𝒑 𝒄𝒂𝒎𝒑 = 𝒚𝑨 𝑪𝒑𝑨 + 𝒚𝑩 𝑪𝒑𝑩 + 𝒚𝑪 𝑪𝒑𝑪
A B C
Where “y” is mol fraction of the gas in mixture

Mixed ABC

Do you get it??

 Integral Evaluation of Sensible Heat
Chapter 4
𝑇𝐶 𝑇
𝑝
What we know?? න 𝑑𝑇 = න 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 + 𝐷𝑇 −2 𝑑𝑇
𝑇0 𝑅 𝑇0

𝑇2
𝐵 𝐶 𝐷
∆𝐻 = න 𝐶𝑝 𝑑𝑇 = 𝐴 + 𝑇0 𝜏 + 1 + 𝑇02 𝜏 2 + 𝜏 + 1 +
2 3 𝜏𝑇02
𝑇 − 𝑇0
𝑇1

How we get the exact number?? OK,ok.. Here much simpler form for you…
𝑇𝐶 𝑇 𝑇−𝑇0
න
𝑝
𝑑𝑇 = න 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 + 𝐷𝑇 −2 𝑑𝑇 𝜏−1=
𝑇0
𝑇0 𝑅 𝑇0
𝐶𝑝 𝐻 𝐵 𝐶 2 𝐷
= 𝐴+ 𝑇 𝜏+1 + 𝑇 𝜏2 +𝜏+1 +
𝑅 2 0 3 0 𝜏𝑇02

It is still in Integral Equation ∆𝑯 = 𝑪𝑷 𝑯𝒙 (𝑻 − 𝑻0 ሻ

Can we get simpler equation??
 Latent Heat of Pure Subtance
Chapter 4

Lest back to our first case

Can you see the bubles??

 Latent Heat of Pure Subtance
Chapter 4

Lest back to our first case

Amount of energi needed to change
the phase
 Latent Heat of Pure Subtance
Chapter 4

How can we
Here are the equations
know the
number??
4. Watson Eq: 𝐏𝐬𝐚𝐭
1. Clayperon Eq: ∆𝐇 = 𝐓∆𝐕
𝐝𝐓
∆𝐻 = 𝐿𝑎𝑡𝑒𝑛𝑡 𝐻𝑒𝑎𝑡; 0.38
∆H2 1 − Tr2
∆𝑉 = Volume change occupied= phase change;
∆H
𝑃 𝑠𝑎𝑡 = saturated vapor 1 1−
pressure Tr1
(evaluated by Antoine Eq)
∆𝐇
2. Troutons Eq :
5. Using Steam tables
~ 10
(only for water)
𝐑𝐓𝐧
Tn is absolut boiling point.
∆𝐻𝑒𝑣𝑎𝑝 = 𝐻𝑣 − 𝐻𝑙
3. Riedel Eq :
∆𝑯 𝟏,𝟎𝟗𝟐 (𝒍𝒏 𝑷𝒄−𝟏,𝟎𝟏𝟑ሻ
=
𝑹𝑻𝒏 𝟎,𝟗𝟑𝟎−𝑻𝒓𝒏
Pc is critical pressure and Trn is reduced temperature.(Tr = T/Tc)
 Heat of Reaction
Chapter 4

Consider this reaction

1 3
𝑁 + 𝐻 ⟶ 𝑁𝐻3 ∆𝐻 = −46,110 𝐽
2 2 2 2

∆𝐻 = Δ𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − Δ𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡

Actual T of materials
𝑇2
∆𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑜𝑟 ∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = න 𝐶𝑝 𝑑𝑇
𝑇1
T reference, usually 25 C
 Standard Heat of Reaction
Chapter 4

Consider this reaction

Exothermic reaction
1 3 0
𝑁 + 𝐻 ⟶ 𝑁𝐻3 ∆𝐻298 = −46,110 𝐽
2 2 2 2

Standard heat of reaction is written as ∆H298

0
, 298
means this heat were calculated at 298,15 K
What
Andis What
the meaning
is standard
of this
condition?
symbol?

Standard Condition :
- Gas : Pure subtance in ideal gas condition at Pressure 1 bar
- Liquid dan solid : Pure subtance in real condition at
Pressure 1 bar.
 Standard Heat of Formation
Chapter 4

Consider this reaction

Which one is formation reaction?
1
𝐶 + 𝑂2 + 2𝐻2 → 𝐶𝐻3 𝑂𝐻 Generally formation reaction is written in form of :
2
0
𝐶 𝑠 + 𝑂2 𝑔 → 𝐶𝑂2 𝑔 ∆𝐻𝑓298 = −339,509 𝐽

𝐻2 𝑂 + 𝑆𝑂3 → 𝐻2 𝑆𝑂4

• 𝑓 stand for “formation”

• The chosen condition is T 298.15 K or
25℃
Definition :
Formation reaction was defined as reaction to produce
1 compound from its molecular element, in which the
product is 1 mole in amount as basis
 Standard Heat of Formation
Chapter 4

Calculate the heat of reaction from reaction below

𝐶𝑂2 𝑔 + 𝐻2 𝑔 → 𝐶𝑂 𝑔 + 𝐻2 𝑂 𝑔

Break down the reaction to get heat of formation of each compound

0 Wait, waittt Where is H2??

𝐶𝑂2 𝑔 → 𝐶 𝑠 + 𝑂2 𝑔 ∆𝐻𝑓298 = 339,509 𝐽
1 0
𝐶 𝑠 + 𝑂2 𝑔 → 𝐶𝑂 𝑔 ∆𝐻𝑓298 = −110,525 𝐽
2
1 0
𝐻2 𝑠 + 2 𝑂2 𝑔 → 𝐻2 𝑂 𝑙 ∆𝐻𝑓298 = −285,830 𝐽

𝐻2 𝑂 𝑙 → 𝐻2 𝑂 𝑔 0
∆𝐻𝑓298 = 44,012𝐽 Answer :
H2 is only constructed from 1 kind of
0
𝐶𝑂2 𝑔 + 𝐻2 𝑔 → 𝐶𝑂 𝑔 + 𝐻2 𝑂 𝑔 ∆𝐻298 = 41,66 𝐽 element, so its ∆Hf298
0
=0
 Standard Heat of Combustion
Chapter 4

Definiton : Heat of Combustion (enthalpy of combustion) of a substance is the heat liberated

when 1 mole of the substance undergoes complete combustion with oxygen at constant pressure.

Have you ever heard methanol gel?

Wedding party food heater

 Standard Heat of Combustion
Chapter 4

The use of heat of combustion

4𝐶 𝑠 + 5𝐻2 𝑔 → 𝐶4 𝐻10 𝑔
0
• 4𝐶 𝑠 + 4𝑂2 𝑔 → 4𝐶𝑂2 𝑔 ∆𝐻𝑓298 = 4 𝑥(−339,509ሻ𝐽
0
Wait sir, C and H just only consist of • 5𝐻2 𝑔 + 2,5 𝑂2 𝑔 → 5𝐻2 𝑂 𝑙 ∆𝐻𝑓298 = 5 𝑥(−285,830ሻ 𝐽
1 element… How can I know its 0
• 4𝐶𝑂2 𝑔 + 5𝐻2 𝑂 𝑙 → 𝐶4 𝐻10 𝑔 + 6,5 𝑂2 𝑔 ∆𝐻298 = 2877,396 𝐽
0
∆𝐻𝑓298 ?
0
4𝐶 𝑠 + 5𝐻2 𝑔 → 𝐶4 𝐻10 𝑔 ∆𝐻𝑓298 = −125,790 𝐽
 0
Temperature Dependent of ∆𝐻
Chapter 4
Calculating Cp
∆𝑪°𝑷 𝑯 ∆𝑩 ∆𝑪 𝟐 𝟐 ∆𝑫
What about standard reaction at different
𝑹
= ∆𝑨 temperature
+ 𝑻
𝟐 𝟎
𝝉 + 𝟏 + 𝑻or not at 𝝉𝑻𝟐
𝟑 𝟎
𝝉 + 𝝉 + 𝟏 +
𝟎
298,15 K?
∆𝑯° = ∆𝑯°0 + ∆𝑪°𝑷 𝑯 (𝑻 − 𝑻0 ൯
HeatChemical
of reaction at certain
Reaction : temperature can be calculated if the heats of reaction at
i vi A 103B 106C 10-5D
standard
𝑣1 𝐴condition
1 + 𝑣2 𝐴2 +were
⋯→ determined
𝑣3 𝐴3 + 𝑣first
4 𝐴4 + ⋯ CH OH 3 1 2,211 12,216 -3,450 0
CO -1 3,376 0,557 0 -0,031
0
∆𝐻 0 = ෍ 𝑣𝑖 𝐻𝑓𝑖 H2 -2 3,249 0,249 0 0,083
Reference : T = 298,15 K
𝑖
∆𝐴=(1)(2,211)+(-1)(3,376)+(-2)(3,249) = -7,663
∆𝐻0° = °
∆𝐻298 = −200,660 − −110,525
∆𝐵=10,815 x 10-3 ; ∆𝐶=-3,450x10-6 ; ∆𝐷=-0,135x105
𝐶𝑂 𝑔 + 2𝐻 2 → 𝐶𝐻3 𝑂𝐻 𝑔
= −90,135 𝐽
T ∆C°P
T ∆C°P
°
∆H = ∆H0° + R ‫׬‬T dT
0 R
∆H ° = ∆H0° + R ‫׬‬T dT
0 R What about
= -90,135 at T(-1615,5)
+ 8,314 = 800 ℃
T = 800 ℃ = -103,556 J
 Heat Effect of Industrial Reactions
Chapter 4

Process Flow Diagram of Cumene Production

Hmmm,,, I smell Reactor Temperature 377 K

problem here…
 Heat Effect of Industrial Reactions
Chapter 4

1 2
4𝐻𝐶𝑙 𝑔 + 𝑂2 𝑔 → 2𝐻2 𝑂 𝑔 + 2𝐶𝑙2 𝑔 ∆𝐻 = σ𝑙𝑖 𝑛𝑖 𝐶𝑝𝑖
°
(T – 298,15) ∆𝐻

∆𝐻𝑝
° ∆𝑪°𝑷 𝑯
𝐶𝑝𝑖 =𝑅𝑥
𝑹 ∆𝐻𝑅

Total enthalpy change :

°
∆𝐻298
°
∆𝐻 = ∆𝐻𝑅 + ∆𝐻298 + ∆𝐻𝑝

∆𝐻𝑅 = perubahan entalpi reaktan pada suhu T1 ke suhu referens

298,15 K
Material entering reactor ( R ) : HCl, O2
°
Material Out ( P ) : HCl, O2 Cl2, H2O ∆𝐻298 = entalpi reaksi standar pada suhu 298,15 K
∆𝐻𝑝 = perubahan entalpi produk dari suhu referens 298,15 K ke
suhu T
T reference = 298,15 K