UNIT IV

1
Energy balance
• Concerned with energy changes and energy
flow in a chemical process.

Conservation of energy – first law of

thermodynamics

i.e. accumulation of energy in a system = energy

input – energy output

2
 Forms of energy
• Potential energy (mgh)
• Kinetic energy (1/2 mv2)
• Thermal energy – heat (Q) supplied to or removed from a
process
• Work energy – e.g. work done by a pump (W) to transport
fluids
• Internal energy (U) of molecules

m – mass (kg)
g – gravitational constant, 9.81 ms-2
v – velocity, ms-1

3
 Energy balance
W

mass in mass out

system
Hin Hout

4
Uses
• Heat required for a process
• Rate of heat removal from a process
• Heat transfer/design of heat exchangers
• Process design to determine energy requirements
of a process
• Pump power requirements (mechanical energy
balance)
• Pattern of energy usage in operation
• Process control
• Process design & development
• etc
5
Heat Capacity

6
Heat Capacity
Heat capacity, or thermal capacity, is
a measurable physical quantity equal to the ratio of
the heat added to (or subtracted from) an object to the
resulting temperature change
T2

Q = n  C p dT
T1

Where, Q- heat in kJ
Cp- heat capacity at constant pressure
(kJ/kmol.K)
7
The heat capacity of a substance is not constant ;but varies with
temperature. For convenience in engineering calculation,
it is expressed by a polynomial equation such as

C p = a + bT + cT 2
Subs in the eqn for “Q”
T2
 CT 
 
T2 2 3
bT
Q = n  a + bT + CT dT = n aT +
2
+ 
T1  2 3  T1
Where a,b and c are constants
n-Number of moles(kmol)
T –Temperature in K
T2

H =  C p dT
T1

∆H-Change in enthalpy in kJ/kmole

8
Mean Heat Capacity:
Q
C pm =
n[T2 − T1 ]

 2
 
T
1
=  + + 2
C pm a bT cT dT
 [T2 − T1 ]  T1

9
Heat Capacity of Mixtures of Gases
The heat capacity of an ideal gas mixture can be evaluated as the sum
of the heat capacities of the individual constituents each weighted
according to the mole fraction in the mixture. Thus
n
C p ,mixture =  y i C p ,i
i

Where
yi- The mole fraction of component i in the mixture of n components
Cp,iSpecific heat i component in pure state
If the heat capacity can be expressed as a quadratic function of temperature, i.e

C p,mixture =  + T + 
The heat capacity of the mixture is
n
C p ,mixture =  yi C p ,i
i

=   yi  i  +   yi  i T +   yi  i 

10
•Problem-1
•The heat capacity of carbon dioxide is given by the following relation
Cp = 26.540 + 42.454 x 10-3 T - 14.298 x 10-6 T2
where Cp is in kJ/kmol K and T is in K.
[Link] much heat is required to heat 1 kg of CO2 from 300 K to 1000 K?
[Link] the relation expressing the heat capacity in kcal/kmol.°C and temperature
in °C.
[Link] the relationship giving heat capacity in Btu/lb-mol°F & temperature in°F.
Solution
(a) The heat requirement can be computed using the equation dQ = nCp dT (constant
pressure) which on integration gives
T2

Q = n  C p dT
T1
T2 Here n = 1/44 kmol.
 bT 2 CT 3 
 
T2

Q = n  a + bT + CT dT = n aT +
2
+  Therefore,
T1  2 3  T1
 1  −3 1000 − 300  − 6 1000 − 300 

   
2 2 3 3
Q =   26.541000 − 300 + 42.45410   − 14 . 298 10  
 44    2   3 
= 755.85e kJ
11
(b) Let us use the given equation to evaluate the heat capacity at
temperature t °C. The specific heat at this temperature is evaluated by the
given equation as

Cp   −3
    −6

= 26.540 + 42.454 10 T + 273.15 − 14.298 10 T + 273.152

 
= 37.068 + 34.64310 −3 T  − 14.298[10 −6 ][T 2 ]

in the above equation T is in °C. By dividing the equation by 4.1868,

the specific heat evaluated is in kcal/kmol.°C . Hence the desired
equation is
 
= 8.854 + 8.27410 −3 T  − 3.415[10 −6 ][T 2 ]

12
By replacing T in °C in the above equation by T' - 32)/1.8 the
equation becomes

 
C p = 8.7058 + 4.664210 −3 T  − 1.054[10 −6 ][T 2 ]
In the above equation
T =  F and
kcal
Cp =
kmol.K
Btu kcal
Since, =
lb − mol. F kmole.C

The above equation gives Cp in Btu/lb-mol.°F as well, when the

temperature is in °F

13
•Problem-2
The molal heat capacity of CO is given by Cp = 26.586 + 7.582 x
10-3T.- 1.12 x 10-6 T2
Where Cp is in kJ/kmol K and T is in K.

1. Calculate the mean molal heat capacity in the temperature

range of 500-1000 K.
2. CO enters a heat exchanger at a rate of 500m3 per hour at
STP. Calculate the heat to be supplied to the gas to raise
its temperature from 500 to 1000 K.
3. CO is to be heated from 500 to 1500 K. What percent error
is expected if the heat requirement is calculated using the
mean heat capacity value determined in part (a)?

14
Solution
•(1) Mean molal heat capacity
 1 2
 
T

=   a + bT + cT dT
2
C pm
[T2 − T1 ]  T1
 1 
C pm =
b  2
 2 c  3
 3 
 a T2 − T1  +   T2 − T1 +   T2 − T1   
[T2 − T1 ]   2 3 
 
 7.58210 −3 1000 
 1.1210 −6 
  
26.5861000 − 500 + 
1
= 
2
− 500 − 
2
 1000 3
− 500 3

1000 − 500   2   3  

kJ
= 31.293
kmol.K

15
2)Moles of gas to be heated by using ideal gas law
(

n=
PV
=
1500 = 22.32 kmol
RT 0.08206273 hr

Heat to be supplied
Q = nC pm (T2 − T1 )

= 22.3231.2931000 − 500 = 3.49210

kJ
hr
 
5

(c) The mean heat capacity calculated in part (a) is valid for the
temperature range of 500-1000 K. Heat requirement calculated using
the mean heat capacity calculated in part (a) is

= 22.3231.2931500 − 500 = 698.6

kJ
hr

16
Actual heat requirement is

Q=
22.32 
  −  +
 
 7.58210 −3  2
− 2

−
 
 1.1210 − 6  3
− 3


26 . 586 1500 500   1500 500   1500 500
1500 − 500   2   3  

= 735.6
kJ
hr

Percent error:
 735.6 − 698.6 
=  100 = 5%
 735.6 

17
•Problem-3
Combustion of solid wastes produces a flue gas of the following
analysis: CO2 = 9.0%, CO = 2.00%, O2 = 7.00% and N2 = 82.0%.
Find the difference in enthalpies for this gas between the bottom
and top of the stack if the temperature of the gas at the bottom is
600 K and that at the top is 375 K. The heat capacities of the gas
are:
CO2 : Cp = 26.540 + 42.454 x 10-3 T - 14.298 x 10-6 T2
CO : Cp = 26.586 + 7.582 x 10-3 T - 1.12 x 10-6 T2
O2 :Cp = 25.74 + 12.987 x 10-3 T - 3.864 x 10-6 T2
N2 : Cp = 27.03 + 5.815 x 10-3 T - 0.289 x 10-6 T2
Cp is in kJ/kmol K and T is in K.

18
Solution:
The heat capacity
n
of the mixture is
C p ,mixture =  y i C p ,i
i

=   y i  i  +   y i  i  +   y i  i 

y1 0.09 α1 26.54 β1 42.454x10-3 Γ1 -14.298x10-6

y2 0.02 α2 26.586 β2 7.582x10-3 Γ2 -1.12x10-6

y3 0.07 α3 25.74 β3 12.987x10-3 Γ3 -3.864x10-6

y4 0.82 α4 27.03 β4 5.815x10-3 Γ4 -0.289x10-6

 y   = 0.0926.540 + 0.0226.586 + 0.0725.74 + 0.8227.03 = 26.8867

i i

 y   = 0.0942.454 + 0.027.582 + 0.0712.987 + 0.825.81510  = 9.649910 

i i
−3 −3

 y   = −0.0914.298 + 0.021.12 + 0.073.864 + 0.820.28910  = −1.816710 

i i
−6 −6

19
Therefore,
    
C p ,mixture = 26.8867 + 9.649910 −3 T  − 1.816710 −6 T 2

Enthalpy difference between the bottom and top of the stack is

T2

H =  C p dT
T1

 26.8867 + 9.649910 T  − 1.816710 T dT

375
−3 −6
= 2

600

kJ
= −6656.29
kmol
The enthalpy of the gas at the top of the stack is less than that at the
bottom by 6656.29 kJ per kmol of gas.

20
•Problem-4
Determine the heat capacity of Na2SO4·l0H2O at room
temperature using Kopp's rule. The atomic heat capacities of
elements (J/g-atom K) are 26.04 for Na, 22.6 for S, 16.8 for O ,
and 9.6 for H. Compare the result with the experimental value of
the heat capacity of 592.2 J/mol K
Solution
According to Kopp's rule, the heat capacity of of Na2SO4·l0H2O, 2 times the
atomic heat capacity of sodium + atomic heat capacity of sulphur + 14 times the heat
capacity of oxygen + 20 times the atomic heat capacity of hydrogen.
Therefore,
Heat capacity of of Na2SO4·l0H2O = [2][26.04] + 22.6 + [14][16.8] + [20][9.6]
= 50l.9 kJ/mol K
The heat capacity predicted using Kopp's rule deviates from the experimental value by

 592.2 − 501.9 
=  100 = 15.25%
 592.2 

21
•Problem-5
Enthalpy of steam at 75 kPa and 573 K is 3075 kJ/kg referred to
liquid water at 273 K. If the mean heat capacity of liquid water and
water vapour are 4.2 kJ/kg K and 1.97 kJ/kg K respectively,
calculate the heat of vaporization of water at 75 kPa. The
saturation temperature of water at 75 kPa is 365 K.
Since the boiling point of water at 75 kPa is 365 K, the vapour at 573 K
and 75 kPa is superheated steam. Take mass as 1kg
Step:1 Step:2 Step:3

Water at Water at Steam at Steam at

75kPa, 75kPa, 75kPa, 75kPa,
273K 365K 365K 573K

Process of converting liquid water to superheated steam

22
Step 1: Water is heated from 273 K to 365 K at constant pressure. Enthalpy change,
∆H1 =mCp∆T

= 14.2365 − 273 = 386.4kJ

Step 2: The liquid is vaporized at constant pressure and constant temperature.
H 2 = H v = m
λ-latent heat
Step 3: The saturated vapour at 365 K is heated to 573 K at constant pressure.
∆H3 =mCp∆T

= 11.97573 − 365 = 409.76kJ

Assuming that the enthalpy of liquid water at 273 K to be zero, then the enthalpy of
the superheated steam in the final state is
o +∆H1 +∆Hv + ∆H3=∆H
Therefore,
∆Hv= 3075 - 386.4 - 409.76 = 2278.84 kJ
Therefore, the heat of vaporization of water at 75 kPa is 2278.84 kJ.

23
•Problem-6
The gas having the following composition is at temperature of 750
K. SO2 = 7%, O2 = 11%, SO3 = 1% and N2 = 81%.Calculate the
heat content of 2 kgmol of gas mixture over 300 K using heat
capacity data given below

24
Solution:
Basis: n=2kmole of gas mixture
n
C p ,mixture =  y i C p ,i
i

=   y i  i  +   y i  i  +   y i  i 

y1 0.07 α1 43.46 β1 10.64x10-3 Γ1 -5.95x10-6

y2 0.11 α2 26.01 β2 11.76x10-3 Γ2 -2.34x10-6

y3 0.01 α3 22.03 β3 121.63x10-3 Γ3 -91.87x10-6

y4 0.81 α4 29.60 β4 -5.15x10-3 Γ4 -13.19x10-6

 y   = 0.0743.46 + 0.1126.01 + 0.0122.03 + 0.8129.6 = 30.09

i i

 y   = 0.0710.64 + 0.1111.76 + 0.01121.63 − 0.815.1510  = −0.9110 

i i
−3 −3

 y   = −0.075.95 + 0.112.34 + 0.0191.87 + 0.8113.1910  = −12.2810 

i i
−6 −6

25
Therefore

    
C p , mixture = 30.09 − 0.9110 −3 T  − 12.2810 −6 T 2

Enthalpy difference between the bottom and top of the stack is

T2

Q = n  C p dT
T1

    
750
Q = 2  30.09 − 0.9110 −3 T  − 12.2810 −6 T 2 dT
300

= 23418.3kJ

26