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ENERGY BALANCE FOR

NONREACTIVE PROCESSES

part 1

Elements of energy balance equations

4.1

 a. Reference states b. Hypothetical process paths c. Procedure for energy balance calculations

4.2 Changes in pressure at constant temperature 4.3 Changes in temperature

a. Sensible heat and heat capacities

b. Heat capacity formulas

c. Estimation of heat capacities

d. Energy balance on single phase systems

4.1 Elements of energy balance equations

Reference
state
 • A common practice is to arbitrarily designate a reference state for a substance at which U or H is declared to equal zero. • Then tabulate U and/or H for the substance relative to the reference state. • U and H are state properties of a species; their values depend only on • the state of the species – primarily on its temperature • and state of aggregation (solid, liquid or gas) • and, to a lesser extent, on its pressure (and for mixtures of some species, on its mole fraction in the mixture).
State
properties
Process path

Construct a hypothetical process path from the initial state to the final state consisting of a series of steps.

When a species passes from one state to another, both

U and H for the process are independent of the path taken from the first state to second one

2

Example

Compressing H 2 gas
from 1 atm to 300
atm at 25 o C
Melting ice at 0 o C
and then heating
the liquid water to
30 o C all
Mixing sulfuric acid
and water at a
constant
temperature of
Phase changes at
constant T and P-
20 o C and a constant
pressure 1 atm
melting, solidifying,
Changes in P at constant
T and state of
vaporizing,
condensing,
aggregation
sublimating
Mixing of two liquids or
dissolving of a gas or a
solid in a liquid at
constant T and P
Changes in T at constant
P and state of
aggregation

c. Procedure for energy balance

calculations

Perform all required material balance calculations

Write appropriate form of the energy

balance (closed or

open system)

Calculate all required

values of Ui or Hi and

insert values in the appropriate places in the table

For an open system, construct a table with columns for inlet and outlet stream

component flow rates

and specific enthalpies relative to the chosen

reference state.

Choose a reference state - phase, T, P - for

each of the species

involved in the process

For a closed constant volume system,

construct a table with columns for initial and final amounts of each species and specific

internal energies

relative to the chosen reference state.

Calculate Q for open or close

system

Calculate any work, kinetic energy, or potential energy terms that you have

not drop from the energy balance

Solve the energy balance

for whichever

4

4.2 Changes in pressure at constant

temperature

If the pressure of a solid or liquid changes at

constant T,

U = 0

H = [U + (PV)] = [U + PV + V P] = [V P]

Both U and H independent of pressure for ideal

gases may assume Δ U = 0 and Δ H = 0 for a gas

undergoing an isothermal pressure change unless

gas temperature below 0 0 C or

well above 1 atm are involved.

4.3 Changes in temperature

a. Sensible heat and heat capacities

The term sensible heat signifies that heat must be transferred to raise or

lower the temperature of a substance or mixture of substances.

The quantity of heat required to produce a temperature change:

Q = U

(closed system)

Q = H

(open system)

Heat capacity at constant volume C v . At constant volume:

^

T

2

U C T dT

v

T

1

Suppose both temperature and the volume
of a substance change. To calculate U –
break the process into 2 steps ( a change in
V at constant T followed by a changes in T
and constant V):
^
^
U
U
1
2
A T ,V

A T ,V

A T ,V
1
1
1
2
2
2
^
^
^
  
U
U
U
1
2

For ideal gas and (to a good approximation) liquid and solids, U depends only on T. In step 1, T is constant, U 1 = 0.

Step 2 V is constant:

T
^

2

U C T dT

v

T

1

Ideal gas: Exact Solid or liquid: good approximation Non ideal gas: valid only if V is

constant

Heat capacity at constant pressure C p . At constant pressure:

^ T

2

H C T dT

p

T

1

For first step refer section 8.2 (Felder), as T is constant, H 1 = 0 (for ideal gas), H 1 = V P (for solid or liquid).

Step 2 P is constant:

^

H

^

T

2

 

V P C T dT

p

T

1

Solid or liquid

^

T

2

H C T dT

p

T

1

Ideal gas: Exact

Non ideal gas: valid only if P

is constant

b. Heat capacity formula

Heat capacities are functions of temperature and frequently expressed in polynomial form (C p = a + bT + cT 2 + dT 3 ).

Liquid and Solids : C
 C
p
v
Ideal Gases
: C
C
R
p
v
R : Gas constant

c. Estimation of heat capacity

Kopp’s rule

simple empirical

method for estimating the

heat capacity of a solid or liquid near

20 0 C.

Rules 1 : For a mixture of gases

or liquids, calculate the total

enthalpy change as the sum of the enthalpy changes for the pure mixture component

For heat capacities of certain mixture

may use these

rules:

Rules 2 : For a highly dilute

solutions of solids or gases in

liquids, neglect the enthalpy change of solute.

For heat capacities of certain mixture: (C p ) mix (T)

C

p

mix

w here

C

y

i

p

C pi

mix



T

all

y C

i

mixture

pi

components



T

heat capacity of mixture

mass or mole fraction of i component

heat capacity of i component

For enthalpy calculation:

^

H

T

2

T

1

C

p

mix



T

dT