Chapter 8 Summary

An integral energy balance (the first law of thermodynamics) for a closed constant-volume system
with no kinetic or potential energy changes (E k = 0, E P = 0) and no energy transferred in or
out as work (W = 0) is:
Q U

n U n U
i

final

initial

For a closed system expanding or contracting against a constant external pressure, the balance is
Q H

n H n H
i

final

initial

For an open system at steady state with negligible kinetic and potential energy changes from inlet
to outlet and no energy transfer as shaft work, the balance is

Q H

n
final

H i ni H i
initial

In these equations n is the amount (mass or moles) of a species in one of its initial or final states
in the process, n is the flow rate (mass or molar) of a species in a continuous stream entering or
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leaving the process, and U and H are respectively the specific internal energy and specific
enthalpy of a species in a process state relative to a specified reference state for the same species.

This chapter presents formulas and methods for evaluating U and H (and hence U, H , and

H ) when tables of internal energies and enthalpies are not readily available. Here is the general
procedure:
1. Choose a reference state (phase, temperature, and pressure) for each species involved in
a process.

2. Choose a path from the reference state to each initial and final (or inlet and outlet)
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process state for each species, and evaluate U i (or H i ) as U (or H ) for the
transition from the reference state to the process state.
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3. Once all of the U i (or all H i ) values are determined in this manner and all of the n i

(or all n i ) values are determined from material balances, densities or equations of state,

and phase equilibrium relations, calculate U, H, or H and substitute the result in the
energy balance to determine whichever variable is unknown (usually the heat, Q, or heat

transfer rate, Q ).

Following are points regarding the implementation of this procedure for various types of
processes.

Energy balance calculations for a system (a process unit or combination of units) are conveniently organized through the construction of an inlet-outlet internal energy table (or

enthalpy table). The table lists n (or n i ) and U (or H ) for each species at each state (phase,
temperature, pressure) in which the species is found in process streams. Once all of these
variable values have been determined and inserted in the table, the subsequent evaluation of

U, H, or H is straightforward.

The fact that internal energy and enthalpy are state properties means that any convenient
process path from a reference state to a process state may be chosen, even if the actual process
proceeds by a different path. As a rule, you would choose a path that allows you to make use
of heat capacities, phase transition temperatures, and latent heats tabulated in an available
reference (like this text)

Changes in pressure at constant temperature. For a species undergoing an isothermal

pressure change, P,
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U 0 for solids, liquids, and nearly ideal gases. For ideal gases, U 0 .

H V P for solids and liquids, where V is the (presumably constant) specific volume of the

solid or liquid.
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H 0 for nearly ideal gases or for moderately small pressure changes (on the order of a few
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atmospheres). For ideal gases, H 0 .

If gases are at conditions at which they are far from ideal or if they undergo large pressure
changes, you must either use tables of thermodynamic properties (such as the steam tables for
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water) or thermodynamic correlations beyond the scope of this text to determine U or H .

Changes in temperature. The specific internal energy of a species increases with increasing
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temperature. If a species is heated at constant volume and is plotted U versus T, the slope of
the resulting curve is the heat capacity at constant volume of the species, Cv'(T), or
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U
Cv
T

. If a species undergoes a change in temperature from T 1 to T2 without

cons tan t ,V

changing phase,

T2

U CV (T ) dT
T1

This equation is
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(a) exact for an ideal gas, even if V changes during the heating or cooling process. (For
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an ideal gas, U does not depend on V )

(b) a good approximation for a solid or liquid.
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(c) valid for a nonideal gas only if V is constant.

The specific enthalpy of a species ( H U PV ) also increases with increasing temperature. If

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a species is heated at constant pressure and H is plotted versus T, the slope of the resulting
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H
curve is the heat capacity at constant pressure of the species, CP(T), or C P
.
T

cons tan t , P

It follows that if a gas undergoes a change in temperature from T 1 to T2 with or without a

concurrent change in pressure,
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T2

H C P (T ) dT
T1

This equation is
(a) exact for an ideal gas, even if P changes during the heating or cooling process. (For an
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ideal gas, H does not depend on P).

(b) valid for a nonideal gas only if P is constant.

If a liquid or solid undergoes a temperature change from T 1 to T2 and a simultaneous

pressure change, P, then
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T2

H V P CP (T )dT
T1

Table B.2 lists coefficients of polynomial expressions for C P(T) [kJ/(mol.C)] at P = 1 atm.
The expressions should be accurate for solids, liquids, and ideal gases at any pressure and for
nonideal gases only at 1 atm.

To determine an expression or value for C v(T) from a known expression or value for C P(T),
use one of the following relationships:
Liquids and Solids: Cv C P
Ideal Gases:

Cv = CP - R

where R is the gas constant. Since the degree unit in the denominator of the heat capacity
is a temperature interval, R can be subtracted directly from the expressions for C P in
Table B.2.

The heat capacity of a solid or liquid can be estimated in the absence of tabulated data
using Kopp's rule.

If only tabulated values of C P or Cv at discrete temperatures are available, the integrals in

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the expressions for U and H must be evaluated by numerical integration, using

formulas such as those given in Appendix A.3.

Phase changes at constant temperature and pressure. Latent heats are changes in
specific enthalpy associated with phase changes at constant T and P. For example, the
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latent heat of fusion (more commonly, the heat of fusion), H m (T , P) , is the enthalpy
change for the process in which a solid at temperature T and pressure P becomes a liquid
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at the same temperature and pressure, and the heat of vaporization, H V (T , P) , is H

for the process in which a liquid at T and P becomes a vapor at the same T and P.

Table B.1 lists standard heats of fusion and vaporization for a number of species, or
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H m and H V , at the normal melting and boiling point temperatures (P = 1 atm),

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which are also listed in Table B.1. If latent heat data are not available for a species, H m
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and H V , may be estimated using formulas given.

You can use the formulas given above to determine the specific enthalpy of any species in
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one state relative to that species in any other state. For example, to calculate H for
benzene vapor at temperature 300C and 15 atm relative to solid benzene at a reference
state of -20C and 1 atm, you would carry out the following steps.
1. Heat the solid from the reference temperature (-20C) to its normal melting point Tmp,
which from Table B.1 is 5.53C.

H1

5.53

20.0

(C P ) solid dT

(C P)solid is not listed in Table B.2, so it must either be found elsewhere or estimated
using Kopp's rule. The latter provides a crude approximation but a very reasonable one
to make in this case, considering how little this step will contribute to the overall
enthalpy change.
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2. Melt the solid at Tmp. H 2 H m (5.53C), which from Table B.1 is 9.837 kJ/mol.
3. Heat the liquid from Tmp to the normal boiling point, Tbp, which from Table B.1 is 80.10C.
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80.1

H 3 (CP ) liquid dT
5.53

A polynomial formula for (C P)liquid is given in Table B.2. Since it applies to T expressed in
kelvin units, the limits of the integral should be changed to their kelvin equivalents.

4. Vaporize the liquid at T bp. H 4 H V (80.1C), which from Table B.1 is 30.765 kJ/mol.

5. Heat the vapor from Tbp to 300C.

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300

H 5 (CP ) vapor dT
80.1

A formula for (CP)vapor is given in Table B.2.

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6. Bring the vapor from 1 atm to 15 atm at 300 C. H 0 as long as the vapor behaves like an
ideal gas, which it would at this high temperature.
7. Add the enthalpy changes for each of the preceding steps to calculate the desired specific
enthalpy.

The psychrometric chart (or humidity chart) contains values of a number of process variables
for air-water vapor systems at 1 atm. The values listed on the chart include dry-bulb temperature (the temperature measured by common temperature-measurement instruments),
moisture content or absolute humidity (mass ratio of water vapor to dry air), relative humidity,
humid volume (volume per mass of dry air), wet-bulb temperature (the temperature reading
on a thermometer with a water-saturated wick around the bulb immersed in a flowing stream
of humid air), and enthalpy per mass of dry air. If you know the values of any two of these

variables for humid air at or near 1 atm, you can use the chart to determine the values of the
other four, which can greatly simplify material and energy balance calculations.

In adiabatic cooling operations, a stream of warm gas is brought into contact with a stream of
cold liquid, causing the gas to cool and some liquid to evaporate. If (a) the gas is dry or humid
air, the liquid is water, and the process takes place at about 1 atm, (b) the process is adiabatic,
(c) the heat capacities of liquid water, water vapor, and air can be considered constant over the
temperature range of the process, and (d) enthalpy changes associated with temperature
changes of the liquid may be neglected, then the final state of the air must lie on the same wetbulb temperature line as the state of the inlet air on the psychrometric chart.

An enthalpy change known as the heat of mixing or heat of solution is associated with the
mixing of certain liquids (like acids and water) and the dissolving of some gases or solids in a
liquid solvent at a given temperature and pressure. An ideal solution is one for which the heat
of mixing or solution is negligible, so that the enthalpy of the solution is the sum of the
enthalpies of the pure solution components at the same temperature and pressure. All gas
mixtures are ideal, as are mixtures of structurally similar liquid compounds (like benzene,
toluene, and xylene). Table B.11 gives heats of mixing at 25C and 1 atm for aqueous sulfuric
acid solutions and heats of solution at the same temperature and pressure for aqueous
solutions of HCl(g) (hydrochloric acid) and NaOH(s) (caustic soda).

To perform energy balance calculations on processes involving nonideal solutions, take the
pure components at 25C as references. To determine the specific enthalpy of a feed or prod uct solution, look it up on an enthalpy-concentration chart if one is available. Otherwise,
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form the solution at 25C [ H H s (25o C ) ] and heat or cool it to its state in the process
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( H CP dT ). For the latter step, either find heat capacity data for the solution or (for
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dilute solutions) assume that the heat capacity is that of the pure solvent.