CE10167 Chemical Engineering Principles

Energy Balances

Lecture 3

Effect of Temperature on Enthalpy & Internal Energy

Heat Capacity (Specific Heat)
Reference State
Multicomponent Mixtures

Study: Felder & Rousseau (3rd Ed.): 325-332; 366-373.

(2nd Ed.): 309-316; 341-354.
CE10167 Energy Balances: Lecture 3

Enthalpy & Internal Energy as Functions of Temperature

(1) Does Enthalpy (or Internal Energy) depend on temperature?

(2) Is such a dependence strong?......or weak?
(3) How much energy is needed to raise the temperature of 1 kg of water
- from 0 to 30oC?
- from 30 to 60oC?

(4) Do we need the same amount of energy to raise the temperature of

1 kg of iron and 1 kg of water by 10oC?

Heat Capacity (Specific Heat)

As chemical engineers we need to know a property that will
enable us to compare quantitatively the energy storage
capabilities of various substances.
This property is known as heat capacity or specific heat.

The heat capacity is defined as

the energy required to raise the temperature of a unit
(mass or mole) of a substance by one degree.

Units: [J/(kg K)] or [J/(mol K)]

Two Types of Heat Capacities: Cv and Cp

Cv , heat capacity at constant volume
Heating (or cooling) at constant volume

U
U

kJ/kg

U dU

CV (T) lim

T 0 T
dT V
dU Cv(T)dT

Cv allows us to calculate the

T (oC, K)

Cv is used for

change in with temperature

at constant volume

Systems

Two Types of Heat Capacities: Cv and Cp

Cp , heat capacity at constant pressure
Heating (or cooling) at constant pressure

kJ/kg

H dH

C p(T) lim

T 0 T
dT P
dH C p(T)dT

Cp allows us to calculate the

T (oC, K)

Cp is used for

change in with temperature

at constant pressure

Systems

Calculation of Specific Enthalpy and Internal Energy

T2

U Cv dT

For process where V is constant

T1

T2

H C p dT

For process where P is constant

T1

Simple relationship exists between Cp and Cv in two cases:

For solid or liquid

Cp Cv

For ideal gases

Cp = Cv + R

R is the Gas Constant

R = 8.314 J/(mol K)

See section 8.3 in

F&R for more details

Heat Capacity as a Function of Temperature

It is commonly expressed as a polynomial function of temperature
e.g.

Cp (T) a bT cT dT
2

See F&R 2nd & 3rd,

Table B-2

T2

H C p(T)dT
T1
T2

H (a bT cT 2 dT 3 ) dT
T1

b 2

H a(T2 T1 ) (T2 T12 )

2

T1 and T2 here
are used in oC

Mean Heat Capacity

Definition

H
C p(T)
T2 T1
U
Cv(T)
T2 T1

How to use

How to calculate

H C p T2 T1

T2

C (T)dT
p

U Cv T2 T1

H mH
U mU

C p(T)

T1

T2 T1

Example 1-L3: Calculation of Internal Energy Change

Calculate the heat required to raise the temperature of 200 kg of nitrous
oxide from 20oC to 150oC in a constant volume vessel. Heat capacity of
nitrous oxide is expressed as Cv = 0.855 + 9.42 x10-4 T (kJ kg-1C-1).
T2

150

T1

20

U Cv dT (0.855 9.42 104 T )dT

U
U 121 kJ / kg

Q U mU
Q 200 121 24200 kJ

Is this the right final answer?

Sources of Enthalpy Data

Calculation based on heat capacities

Thermodynamic tables, e.g. Steam Tables

Thermodynamic charts

Computer databases e.g. Aspen, PPDS

Reference State (Reference Conditions)

It is impossible to determine absolute values of specific
enthalpies (or internal energies).
All values of specific enthalpies are relative to a zero value
at a defined reference state (T, P, state of system).

E.g.

In Steam Tables the reference state is:

liquid water at the triple point
T = 0.01oC and P = 0.00611 bar
= 0 and 0

CAUTION : If two different sources of enthalpies are used we have

to be sure that the reference states are the same!

Multi Component Mixtures Enthalpy

If there is no heat of mixing chemicals:

H mix xi H i

xi

mass/mol fraction of a component i

mi

mass flow rate of component i, [kg/s]

all i

H mix mi H i
all i

H mix ni H i
all i

ni molar flow rate of component i, [mol/s]

i

specific enthalpy of component i

in stream, [kJ/kg or kJ/mol]

We have assumed that specific enthalpies of component i

alone and in the mixture with other compounds are . . .

Example 2-L3:
Energy Balance on Two-Component Mixture Heating
A liquid stream containing 80.0 wt% ethane(C2H6) and 20.0 wt% butane
(C4H10) is heated from 150 K to 200 K at a pressure of 10 bar. Calculate
the required heat input for 1 kg/s of the mixture stream, neglecting
potential and kinetic energy changes. Specific enthalpies are given below.

T2 200 K

H
C2H6 434.5 kJ/kg

H
130.2 kJ/kg

T1 150 K

H
C2H6 314.3 kJ/kg

H
30.0 kJ/kg
C4H10

C4H10

(1) Draw a diagram

1.0 kg/ s at 150 K, 10 bar
0.8 kg/ s C2 H 6
0.2 kg/ s C4 H 10

1.0 kg/ s at 200 K, 10 bar

0.8 kg/ s C2 H 6
0.2 kg/ s C4 H 10

Example 2-L3:
Energy Balance on Two-Component Mixture Heating (cont.)
(2) Write energy balance

H EK EP Q WS
H Q

m H
i

outlet
species

m H
i

inlet
species

(3) Complete energy balance

H Q
Required heat input (for 1 kg/s) is = 116.2 kJ/s

Heat Capacity of a Mixture

p mix

y i Cpi
Heat capacity of
the i-th component

all mixture
components

Heat capacity
of the mixture

Mass or mole
fraction of the i-th
component

T2

C T
p

mix

dT

T1

Example 3-L3: Enthalpy of a Mixture (adapted from F&R, 3rd ed, p.373)
100 mol/h of a stream containing 40 vol.% C2H6 and 60 vol.% C3H8 is heated
from 0oC to 200oC at a constant pressure. Calculate: (a) the heat capacity of
the mixture, and (b) the heat required for this heating process.

Q nH n C p mix dT
200

Example 3-L3: Enthalpy of a Mixture (cont.)

(a)

p mix

0.4 C p C 2 H 6 0.6 C p C 3H 8

p mix

Cp values from Table B.2 p. 635

Units: kJ/(mol oC); Tref = oC

0.4 0.04937 13.92 105 T 5.816 108 T 2 7.28 1012T 3

0.6 0.06803 22.59 105 T 13.11108 T 2 31.711012T 3

p mix

0.06057 19.12 105 T 10.19 108 T 2 21.94 1012T 3

T2

(b) H C p(T)dT
T1

b
c
d
H a(T2 T1 ) (T22 T12 ) (T23 T13 ) (T24 T14 )
2
3
4

Calculate (at home)

Answer : Q nH 1568 kJ / h