CHE 3010 - Thermodynamics of Chemical Processes

Venkat Padmanabhan, PhD

Department of Chemical Engineering
Tennessee Tech University

Lecture 31 - Chapters 4-6 — Review

11/13/2017

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 Heat Capacity
CP
= A + B T + C T 2 + DT −2
R
T2
CP
∫T
Q = ΔH = R dT
R
1

( T1T2 )
T2
CP B 2 C 3 T2 − T1
∫T
2 3
dT = A(T2 − T1) + (T 2 − T 1 ) + (T2 − T1 ) + D
R 2 3
1

Ideal-gas-state heat capacity of a mixture is the mole-fraction-weighted

sum of heat Capacities of individual gases

CPmi x = yACPA + yBCPB + yC CPC

A, B, C, and D for the mixture are given by the mole-fraction-weighted

sums of the coefficients for the pure species
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 Example

P31.1 — A gas mixture contains 60% propane and 40% n-butane at 350
K. Assuming ideal gas state, calculate the heat capacity of the gas
mixture. What is the amount of heat (per mole) required to raise the
temperature of the gas mixture from 350 K to 500 K?

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 Example

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 Example

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 Trouton’s Rule
ΔHn
∼ 10 Tn is the absolute temperature of the normal boiling point
R Tn

Riedel Equation

ΔHn 1.092(l n Pc − 1.013) Trn is the reduced temperature Tn

=
R Tn 0.930 − Trn Pc is the critical pressure in bars

Watson’s Method
0.38
1 − Tr 2
ΔH1 ( 1 − Tr1 )
ΔH2
=

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 Example

P31.2 — 100 kmol/hr of subcooled liquid methanol at 300 K and 3 bar is

superheated to 500 K in a steady-flow heat exchanger. Estimate the
exchanger duty in kW. Saturation temperature of methanol at 3 bar is
368 K.

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 Example

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 Example

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 Formation Reaction

A reaction that forms a single compound from its constituent elements

1
C + O2 + 2H2 → CH3OH
2

C + O2 → CO2
1
C + O2 → CO
2
H2O + SO3 → H2 SO4 Not a formation reaction

Formation reaction are understood to produce 1 mole of product

Heat of formation is therefore based on 1 mole of the compound formed

Reference T is usually 25oC or 298.15 K ΔHfo Data found in

298 handbooks

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 Heat of Reaction ΔHo

4HCl(g) + O2(g) → 2H2O (g) + 2Cl 2(g)

ΔHo = 4(-ΔHof[HCl]) + 1(-ΔHof[O2]) + 2(ΔHof[H2O]) + 2(ΔHof[Cl2])

ΔHo = (-4)(ΔHof[HCl]) + (-1)(ΔHof[O2]) + 2(ΔHof[H2O]) + 2(ΔHof[Cl2])

The stoichiometric coefficients of reactants have a negative sign and

those of the products have a positive sign in front of them

n1 A1 + n2 A2 + … → nx Ax + nx+1 Ax+1 + …

n1, n2, …, nx, nx+1, … are positive numbers

Put a negative sign in front of n1, n2, …, nx-1.

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 Temperature dependence of ΔHo

ΔHo0 — Std. heat of

reaction at a reference T

∑
ΔA = n i Ai Analogous definitions for ΔB, ΔC, and ΔD
i

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 Example

P31.3 — Calculate the standard heat of the following reaction at 500oC:

H2S(g) + 2H2O(g) → 3H2(g) + SO2(g)

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 Example

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 Example

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 Heat Engines

Application of the second law is very important in the study of heat

engines
|QH|

Boiler

| Wnet | = | QH | − | QC |
|Win| |Wout|
Pump Turbine

| Wnet | QC |
η= = 1−
| QH | | QH |

Condenser

η = 100%, if |QC| = 0; but heat |QC|

is always rejected
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 Carnot Engine

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 Entropy changes for the ideal-gas state

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 Open System

Entropy balance for open systems

· + d(mS)V dSS ·
Δ(Sm) F + = SG ≥ 0
dt dt
·
dSS Qj The negative sign indicates change in
∑ Tσ,j
= − entropy of the surroundings with respect
dt j to the system
·
d(mS)V Qj ·
· +
∑ Tσ,j
Δ(Sm) F − = SG ≥ 0
dt j

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 Ideal Work

[( ) ]
1 2 · · ·
Δ H + v + zg m = Q + Ws
2
F
For a stead-state reversible flow process,

[( ) ]
1 2 · · ·
Δ H + v + zg m = TσΔ(Sm)F + Wideal or
2
F

[ ( ) ]
· 1 2
Wideal = Δ H + v + zg m· ·
− TσΔ(Sm) F
2
F

In most chemical processes, the K and P energy terms are negligible

· · − T Δ(Sm)
·
Wideal = Δ(Hm)F σ F
·
If there is only a single stream, Wideal = ΔH − TσΔS
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 Thermodynamic efficiency, ηt
·
If Wideal is positive, work is done ON the fluid, the minimum work required
·
is smaller that the actual work Ws
·
Wideal
ηt = · work required
Ws
·
If Wideal is negative, work is done BY the fluid, the maximum work
·
obtainable is larger that the actual work Ws
·
Ws
ηt = · work produced
Wideal

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 Example

P31.4 — A refrigeration system cools a brine from 25oC to -15oC at the

rate of 20 kg/s. Heat is discarded to the atmosphere at a temperature of
30oC. What is the power requirement if the thermodynamic efficiency of
the system is 0.27? The specific heat of the brine is 3.5 kJ/kgK.

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 Example

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 Lost Work

· · ·
Wlost = TσΔ(Sm)F − Q

For a steady-state flow process,

·
· · Q · · ·
SG = Δ(Sm)F − or TσΔ(Sm)F = Tσ SG + Q
Tσ
· ·
Wlo st = Tσ SG
· ·
The second law of thermodynamics states that SG ≥ 0 Wlo st ≥ 0

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