ChE 413

ChE Thermodynamics
Definitions and The First Law of Thermodynamics
Thermodynamics

Power developed from heat

Initial applications were to heat engines

Calculation of heat and work
requirements for physical & chemical
processes
Definitions

Force
SI unit: newton, N
F = m*a

Temperature
Thermometer can indicate the degree of
hotness by the length of the fluid column
Celsius scale, Kelvin scale
 T(C) = T(K) - 273.15
Fahrenheit scale, Rankine scale
 T(F) = T(R) - 459.67
Definitions

Volume
V = length * width * height

Pressure
Normal force exerted by a fluid per unit area
of the surface
P = F /A unit: pascal (Pa = N/m2)
Definitions

Work
Performed when force acts through a distance
dW = F dl
Work accompanies a change in the volume of
a fluid
V2
W = PdV
V1
Definitions

Energy
Kinetic energy
Potential energy

Heat
Energy in transit
Heat flows from higher temp to lower one
Rate of heat transfer temp. difference
Units: joule (J) , calorie (cal), British thermal
unit (Btu)

Internal energy
Refers to energy of the molecules making up
the substance
1st Law of thermodynamics

Although energy assumes many forms, the total
quantity of energy is constant, and when energy
disappears in one form it appears simultaneously in
other forms.
(energy of system) + (energy of surroundings) = 0

The total energy change of a constant mass system

equals the net energy transported into it as heat
and work
U = Q + W

Enthalpy
H = U + PV

In differential form
dH = dU + d(PV)

Upon integration
H = U + (PV)

Example
Calculate U and H for 1 kg of water when it is
vaporized at constant temperature of 100C and constant
pressure of 101.33 kPa. The specific volumes of liquid and
vapor water at these conditions are 0.00104 and 1.673
m3/kg. For this change heat in the amount of 2256.9 J is
added to the water
Phase rule

J. Williard Gibbs

F = 2-+N
G : number of phases
N : number of chemical species
F : degrees of freedom; number of intensive variables that
must be fixed to establish the intensive state of any system

Example
How many degrees of freedom has each of the following
systems?
a. Liquid water in equilibrium with its vapor
b. Liquid water in equilibrium with a mixture of water vapor &
nitrogen
c. A liquid solution of alcohol in water in equilibrium with its
vapor
Reversible process

A process is reversible when its direction
can be reversed at any point by an
infinitesimal change in external conditions
Constant--V & Constant-
Constant Constant-P processes

For a mechanically reversible, constant
volume, non-flow process
Q = n U

For a mechanically reversible, constant

pressure, nonflow process
Q = n H
Heat capacity

The smaller the temperature change in a body
caused by the transfer of a given quantity of
heat, the greater its capacity

Heat capacity at constant volume
U
CV
T V

Heat capacity at constant pressure

H
CP
T P

For a mechanically reversible constant V
process,
dU = CV dT
T2
Q = nU = n CV dT
T1

For a mechanically reversible constant P

process,
dH = CP dT
T2
Q = nH = n CP dT
T1
Example

An ideal gas is one for which PV/T is a constant,
regardless of the changes it undergoes. Such a gas has
a volume of 0.02271 m3/mol at 0C and 1 bar. In the
following problem, air may be considered as an ideal
gas with the constant heat capacities
Cv = (5/2)R and Cp = (7/2)R

The initial conditions of the air are 1 bar and 25C . It
is compressed to 5 bar and 25C by two different
mechanically reversible processes. Calculate the heat
and work requirements and U and H of the air for
each path.
(a)Cooling at constant pressure followed by heating at
constant volume
(b) heating at constant volume followed by cooling at
constant pressure