CHEE 2331

Chemical Processes

Ch 8: Energy Balance on
Non-Reactive Processes

Department of Chemical and Biomolecular Engineering 1

 Formost practical chemical processes, changes in kinetic and
potential energy, as well as shaft work, can be neglected.

Then, the energy balance for such processes reduces to:

Closed systems: Q=U, for constant volume processes.

Q=H, for constant pressure processes.

Open systems: Q H

For multiple streams in an open system: Q H n i H i
i n i H
outlet inlet
Correspondingly, for multiple species in a closed system:

Q H ni H
i
n H i i Q U n i U
i
n i
i
U

final initial final initial
2
(variable volume)
Remember - State and path functions
PV = znRT, H = f(T)

P1V1T1 (2)
P

(1) P3V3T3
T3, H3
T2, H2
T1, H1
V
W = PV =
d(PV)
State and path functions
PV = znRT, H = f(T)

P1V1T1 (2)
P

(1) P3V3T3
T3, H3
T2, H2
T1, H1
V
W = PV =
d(PV)
Work depends on the path

Likewise, heat depends on the path

But, H = H3 H1 = f(T3) f(T1)

depends on T3 and T1 and is
independent of the path
To find Q, one must calculate H or U.

In absence of tabulated data for H or U, we can construct a convenient

hypothetical path from the initial state to the final state, to calculate H
and U. This can be done because H and U are state functions, i.e.,
H and U are path independent.

The hypothetical path may involve:

Change in P at constant T and state of aggregation.

Change in T at constant P and state of aggregation.
Phase change (e.g., solid to liquid) at constant T and P.
Mixing of two liquids or dissolving of a gas or a solid in a liquid at
constant T and P.
Chemical reaction at constant T and P (to be discussed in chapter 9)

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 CV heat capacity at constant volume. CP heat capacity at constant pressure.

Plot U=U(T) at constant volume. Plot H=H(T) at constant pressure.

Cv is the slope of that curve. CP is the slope of that curve.

U H
U CV H CP
T V T P

T T
U U H H
U U(V, T) dU ( )T dV ( ) V dT H H(P, T) dH ( )T dP ( ) P dT
V T P T
dU dH
For constant volume dV=0, Then C v For constant pressure dP=0, Then CP
dT dT

For liquids and solids: CP CV C

For ideal gases: U and H are functions of temperature only
and CP=CV+R 6
 H dH
CP ( ) P . For P=constant or for ideal gases, H=H(T); thus CP =
T dT
T2

H C P (T)dT
T1

This relation holds exactly for ideal gases (even if P is changing).

It is approximately correct for non-ideal gases. For non-ideal gases this relation
holds exactly for constant pressure (isobaric) operations. And we will assume it is OK
even when gas pressure
changes
If a liquid or solid undergoes a temperature change from T1 to T2 and a simultaneous
pressure change P, then,
T2
^P C (T)dT
V
H
P T1

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Heat capacity as a function of temperature, see Table B.2

CP a bT cT 2 dT 3 or CP a bT cT 2

T2
**VERY different heat
capacities for liquid and
H (a bT cT 2 dT 3 )dT vapor phases**
T1
T2
bT 2
cT dT 3 4
aT
2 3 4 T
1

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

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 U dU
Similarly, CV ( ) V . For V=constant or for ideal gases, U=U(T); thus C V =
T dT
T2

U C V (T)dT: this relation holds exactly for ideal gases.

T1

It is approximately correct for solids and liquids, as well as non-ideal gases.

For non-ideal gases, this relation holds exaclty for constant volume (isochoric) processes.

There is a simple relation between CP and CV for ideal gases:

H U PV H U RT dH dU d(RT) dH dU RdT
C P dT C V dT RdT CP CV R

For ideal gases: Cv 1.5 R, for mono-atomic ideal gases

Cv 2.5 R, for diatomic ideal gases

For liquids or solids: CPCV=C

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The heat capacity of mixtures may be calculated as:

C P,mix (T) yi CPi (T)

i

where yi is the mole (or mass) fraction of the i th component

and C Pi is the heat capacity of that component.

T2

It follows that H P,mix (T)dT.

C
T1

This equation holds when the heat of mixing can be neglected.

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 These formulas provide the
T2 T2
sensible heat associated with changes
U CV dT H CP dT in temperature without phase change or
T1 T1 chemical reactions.

In the presence of phase change one has the latent heat

a) (T, P) Heat of fusion (or heat of melting). Specific enthalpy difference

H M
between the solid and the liquid of a substance at constant T and P. Values
are given in Table B.1 (at the melting point and 1 atm).

H
V (T, P) Heat of vaporization. Specific enthalpy difference
b)
between the liquid and the vapor of a substance at constant T and P. Values
are given in Table B.1 (at the boiling point and 1 atm).

When using the latent heats make sure that the phase change in question
is taking place at the same temperature for which the tabulated value is reported.
Moderate variations of pressure can be ignored.

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 Ideal gas Liquid or solid

Changes in
U 0 0
P
(T const)
H 0 P
V
T2 T2

Changes in

U C
T1
V dt C V dt
T1
T T2 T2
(P const)
H C dt
T1
P C dt
T1
P

T2 T2

Changes in
U C V dt C V dt
both T1
T2
T1
T2
T and P

H C dt
P
V P C P dt
T1
T1
Vaporization/
Melting/Freezing
Condesation
Phase RT
H
H
U V m
change
Const.

H
H
T and P H V m

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Example of Use of Hypothetical Path
Determine H for liquid cyclohexane (CH) at 25 0C, 5 atm. The reference state

is CH vapor at 180 0C and 5 atm. The latent heat of condensation at Tb=80.7 0C
at 1 atm is known.

H

CH(vapor,180 0 C, 5atm) CH(liquid, 25 0 C,5 atm)

P & T H
1 P & T
H
3
2
H

0
CH(vapor, 80.7 C,1 atm) CH(liquid, 80.7 0 C,1 atm)
P & T 0

H
1 & H
3 : Sensible heats 2 : Latent heat of
H
condensation.

H
H H
final H 1 H
2 H
3
ref

80.7 25
^ (5 1)

180
V
Cp,vapor dT H cond C
80.7
p,liquid dT
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 Procedure for Energy Balance Calculations

(see example 8.1-1)

Perform material balance calculations.

Write appropriate energy balance equation, and eliminate negligible terms.
Choose ref. state for each species.
and / or
Construct table with initial and final values of H
U
Calculate H and / or U
and insert into table.

Calculate H and/or U
Calculate work, E K , E P
Find Q.

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Example 8.1-1

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Now choose reference states:

For acetone, choose one of the process stream conditions as the reference state,
value to be brought to zero.
allowing that corresponding

Similarly for N2, can assign a process stream condition as reference state.

**Or for N2, since there is tabulated N2 gas enthalpy data in Table B.8 (uses reference
state of 25oC, 1 atm), we can instead use the TB.8 ref and use values from TB.8

Different editions of the book take different approaches with N2. Reference states
are arbitrary so the resulting calculated energy changes are the same thus
demonstrating the concept of state properties and arbitrary reference states and
hypothetical paths

Here, we will use TB.8 and therefore N2 ref state is 1 atm, 25oC.
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2& 4were calculated by interpolating between points from Table B.8 (where ref is 25 oC, 1 atm)

Note however an alternate and just as valid method would be to calculate the N2 enthalpies
using Cp for N2 from Table B2, in which case you could choose the N2 inlet or outlet condition
as a reference state.

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 Problem 8.54

Stream of cyclopentane vapor flowing at 1550 L/s, 1 atm, 150oC enters a cooler
in which 65% of the feed is condensed at constant Pressure.
a) What is the temperature in the outlet?
b) Fill an inlet-outlet enthalpy table and calculate required cooling rate in kW

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 Heat of Mixing
When a solution is made by mixing a solute (solid, liquid, or gas) with a solvent,
heat may be generated or absorbed. For example when mixing concentrated
sulfuric acid with water, or dissolving NaOH pellets in water, heat is released.

Heat of mixing HS H H SO (so l utio n) (H H SO (l) H H O ) at constant T & P

2 4 2 4 2

Energy balance for mixing process is : Q HS

If HS 0 . Exothermic mixing Q must be removed to keep constant T.

If HS 0 . Endothermic mixing Q must be added to keep constant T.

If Q HS 0 . Ideal solution (const. T) HS 0

Examples of HS 0 : Mixing gases or chemically similar liquids (e.g.,

benzene and toluene).
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Heat of solution: H
S (T, r) is defined as the change in enthalpy for a process
in which 1 mol of solute (gas or solid) is dissolved in r mol of liquid solvent at
constant T.

As r becomes large (r ) then H ( )

approaches a limiting value, H

S S

(infinite dilution).

Heat of mixing: It has the same meaning as the heat of solution but applies for
mixing a liquid solute with a liquid solvent.

Table B.11 all exothermic

* Notes: H S is given in kJ per mol of solute not mol of solution!

Also, the reference state is 25 oC and 1 atm for both water (solvent) & solute.

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Problem 8.97 (old 8.83)

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Ex 8.5-1

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For some common systems, enthalpy data may be directly available from
H-x charts.

1) H-x charts for single liquid phase (binary mixture, i.e., 2 components)
2) Liquid vapor in equilibrium (binary mixture)

Fig. 8.5-1 H2O- H2SO4, mass fractions

in Btu/lbm solution.

H
Reference states: H2SO4 (l) at 77oF , 1 atm
H2O (l) at 32oF , 1 atm

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Example 8.5-2 .

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Adiabatic Mixing:
Energy balance Q H, Adiabatic Q=0
Thus H = 0, requiring the temp to change!
Can be solved using H-x chart.

Q0

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Example 8.5-3

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 H-x charts for vapor-liquid equilibrium (VLE) of
binary mixtures

-Gibbs Phase Rule : DF=2+2-2= 2. Lets specify pressure ( e.g., 1 atm) as

one of the intensive variables.

Specifying one more intensive variable in addition to pressure fixes all

other intensive variables, for example, we can specify temperature, or xA
of either component in either phase.

-Using H-x charts , Flash calculations are similar to the usual VLE phase
diagram analysis discussed before.

Fig. 8.5-2: NH3-H2O VLE

- constant temperature Tie-Lines connect liquid and vapor phase at
equilibrium.

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Flash evaporation: The pressure of a mixture is suddenly reduced (through an
expansion valve) or its temperature is suddenly increased. The mixture
separates into a liquid and a vapor in equilibrium.

Vapor-Liquid
F separator

L
Liquid F: Feed with overall mol fraction xF.
Vapor V: Vapor product with mol fraction xV.
Liquid L: Liquid product with mol fraction xL.

Note: mol fractions refer to the more volatile component of the

binary mixture.
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 Flash evaporation of binary mixture

F = total mol/h of mixture in the feed (given).

The mole fraction of more volatile component in the feed is xF(given).
V= mol/h vapor, mol fraction of more volatile component in vapor is xV.
L = mol/h liquid, mol fraction of more volatile component in liquid is xL.

DoF analysis: Four unknowns: L, V, xV, and xL.

Equations: Overall mass balance, more volatile component mass balance.
Also, for given T and P can find xV and xL from T-xy (or P-xy) curve.

overall : F L V , com ponent : Fx F Lx L V x V

L x xF L x xF
T hen V , V ,
F xV xL V xF xL

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Flash Calculations (1 atm):
F=Feed flow rate
V=Vapor flow rate at exit
L= Liquid flow rate at exit

L x V x F AC

V x F x L AB
L x V x F AC

F x V x L BC

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 Example 8.5-5

Feed: 30 wt. % NH3 solution at 100 psia at 100 lbm/h to a

1-atm flash drum Vapor is 89 wt. % NH3
Determine outlet Temp,
flow rates, composition

100 lb m / h of liquid and Q
Flash mv
0.3 NH 3 Drum 0.89 NH 3
0.7 Water 0.11 Water

F 100 Btu / lb
H V
H

L x ammonia

mL , H L
(1 x L ) w a te r

Q

Relative to same reference conditions used in Fig 8.5-2

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