Advanced Thermodynamics

Note 1
The 1st law and other basic concepts
Lecturer:

Preclassical thermodynamics
(1600s ~ late 1800s)
Galileo (circa 1600) :
thermometry quantification

Joseph Black (1760s) :

the specific heat

Count Rumford (1780s):

mechanical work is an inexhaustible source of caloric
a revival of mechanical concept of heat

Carnot (1824) :

Heat quantity
Energy
Entropy

cyclic operation of an engine - conservation of caloric

Helmholtz (1847) :
conservation of energy

Joule (late 1800s) :

equivalence of mechanical, electrical and chemical energy of heat

Thermodynamics
Their validity lies in the absence of contrary
experience.
It shares with mechanics and electromagnetism a basis
in primitive laws.

Useful equations
Calculation of heat and work requirements for physical
and chemical processes
Determination of equilibrium conditions for chemical
reactions
Determination of equilibrium for the transfer of
chemical species between phases.

Heat and work

Heat always flows from a higher temperature to a
lower one.
Temperature as the driving force for the transfer of
energy as heat.
Heat is never regarded as being stored within a body.
Like work, it exists only as energy in transit from one
body to another.
Unit: calorie is defined as the quantity of heat which
when transferred to one gram of water raised its
temperature one degree Celsius, or, British thermal unit
(BTU) is defined as the quantity of heat which when
transferred to one pound mass of water raised its
temperature one degree Fahrenheit.

Thermodynamics
Classical thermodynamics
natural laws governing the behaviour of
macroscopic systems
First Law

E = Q + W
Internal changes = interactions occurring at boundaries
(T, P, V, etc)

Second Law
Reversible process
Entropy

Heat effect
Work

SYSTEM

Environment/Surroundings

Boundary
(1) adiabatic or diathermal
(2) permeable or impermeable
(3) rigid or movable

An isolated system: impermeable, rigid, adiabatic and independent

of events in the environment

The

st
1

law of thermodynamics

It was first a postulate. However, the

overwhelming evidence accumulated over time
has elevated it to the stature of a law of nature.
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 the system) + (energy of surroundin gs ) = 0

Total internal energy of the system,

depends on the quantity of material
in a system, i.e., the extensive
property.

E = Q + W
U t = Q + W

c.f. intensive property,

e.g. temperature and pressure.
e.g. specific or molar properties

If the gas is heated or cooled, compressed or expanded, and

then returned to its initial temperature and pressure, its
intensive properties are restored to their initial values.
Such properties do not depend on the past history of the
substance nor on the means by which it reaches a given state.
Such quantities are known as state functions.
A state function may therefore be expressed mathematically
as a function of other thermodynamic properties. Its values
may be identified with points on a graph.

When a system is taken from state a to state b along path acb, 100 J of heat
flows into the system and the system does 40 J of work. (1) How much heat
flows into the system along path aeb if the work done by the system is 20J? (2)
The system returns from b to a along path bda. If the work done on the system
is 30J, does the system absorb or liberate heat? How much?
b
c

d
e

t
U ab
= Q +W

= 100 40 = 60 J
= Qaeb + Waeb

Qaeb = 80 J

= Qaeb 20

t
U bat = U ab

= 60 J
= Qbda + Wbda
= Qbda + 30

Qbda = 90 J

Equilibrium
In thermodynamics, equilibrium means not only
the absence of change but the absence of any
tendency toward change on a macroscopic scale.
Different kinds of driving forces bring about
different kinds of change. For example:
imbalance of mechanical forces tend to cause energy
transfer as a work.
temperature differences tend to cause the flow of heat.
Gradients in chemical potential tend to cause substance
to be transfer from one phase to another.

Phase rule
For any system at equilibrium, the number of independent
variables that must be arbitrarily fixed to establish its intensive
state is given by J.W. Gibbs (1875).
The degrees of freedom of the nonreacting systems:
F = 2 + N
where is the number of phases, N is the number of chemical species

A phase is a homogeneous region of matter. A gas or a mixture

of gases, a liquid or a liquid solution, and a crystalline solid are
examples of phases. Various phases can coexist, but they must
be in equilibrium for the phase rule to apply.
The minimum number of degrees of freedom for any system is
zero:
F = 2 + N = 0
N = 1, = 3 (i.e. the triple point)

How many degrees of freedom has each of the following systems:

(1) Liquid water in equilibrium with its vapor.
(2) Liquid water in equilibrium with a mixture of water vapor and nitrogen.
(3) A liquid solution of alcohol in water in equilibrium with its vapor.
(1) 1 species, 2 phases

F = 2 + N = 2 2 +1 = 1
(2) 2 species, 2 phases

F = 2 + N = 2 2 + 2 = 2
(3) 2 species, 2 phases

F = 2 + N = 2 2 + 2 = 2

The reversible process

A process is reversible when its direction can be reversed at any
point by an infinitesimal change in external conditions.

frictionless
never more than differentially removed from equilibrium
traverses a succession of equilibrium states
driven by forces whose imbalance is differential in magnitude
can be reversed at any point by a differential change in external conditions
when reversed, retraces its forward path, and restores the initial state of
system and surroundings

The reversible process is ideal; it represents a limits to the

performance of actual process. Results for reversible processes in
combination with appropriate efficiencies yield reasonable
approximations of the work for actual processes.

Constant-V and constant-P

The general 1st law equation for a mechanically reversible,
closed-system process:

d ( nU ) = dQ Pd (nV )
constant total volume:
Q = n U
the heat transferred is equal to the internal-energy change of the system

constant pressure: dQ = d ( nU ) + d (nPV )

dQ = d [n(U + PV )]

Q = n H
the mathematical definition of enthalphy: H U + PV
the heat transferred is equal to the enthalpy change of the system

Calculate U and H for 1 kg of water when it is vaporized at the

constant temperature of 100 C and the 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 kJ is added to the water.
Imagine the fluid contained in a cylinder by a frictionless piston
which exerts a constant pressure of 101.33 kPa. As heat is added,
the water expands from its initial to its final volume. For the 1-kg
system:
H = Q = 2256.9kJ

U = H P (V )
= 2256.9 J 101.33kPa (1.673 0.001)m 3
= 2256.9kJ 169.4kJ
= 2087.5kJ

Heat capacity
A body has a capacity for heat. The smaller the
temperature change in a body caused by the transfer of a
given quantity of heat, the greater its capacity.
A heat capacity:

dQ
dT

a process-dependent quantity rather than a state function.

Two heat capacities, CV and CP, are in common use for

homogeneous fluids; both as state functions, defined
unambiguously in relation to other state functions.

Heat capacities at ...

At constant volume
U
CV

T V
T2

U = CV dT
T1

At constant pressure
H
CP

T P

(const V )

CV is a state function
and is independent of
the process.

T2

H = C P dT
T1

(const P )

CP is a state function
and is independent of
the process.

Air at 1 bar and 298.15K is compressed to 5 bar and 298.15K by two different mechanically
reversible processes: (1) cooling at constant pressure followed by heating at constant volume;
(2) heating at constant volume followed by cooling at constant pressure. Calculate the heat
and work requirements and U and H of the air for each path.
Information: the following heat capacities for air may be assumed independent of temperature:
CV = 20.78 and CP = 29.10 J/mol.K. Assuming for air that PV/T is a constant, regardless of
the changes it undergoes. At 298.15 K and 1 bar the molar volume of air is 0.02479 m3/mol.
The final volume: V2 = V1 P1 = 0.004958 m 3
P2

(1) The temperature of the air at the end of the cooling step: T = T1

Q = H = C P T = 6941 J
During the second step:

V2
= 59.63 K
V1

U = H PV = 4958 J

U = Q = CV T = 4958 J

The complete process: Q = 6941 + 4958 = 1983 J

U = 0 W = U Q = 1983 J

H = U + ( PV ) = 0
P

2
(2) The temperature of the air at the end of the heating step: T = T1 P = 1490.75 K
1

Q = U = CV T = 24788 J

During the second step: Q = H = C P T = 34703 J

U = H PV = 24788 J

The complete process: Q = 24788 34703 = 9915 J

U = 0 W = U Q = 9915 J

H = U + ( PV ) = 0

Calculate the internal-energy and enthalpy changes that occur when air is changed
from an initial state of 40F and 10 atm, where its molar volume is 36.49 ft3/lb-mole,
to a final state of 140F and 1 atm.
Assume for air that PV/T is constant and that CV = 5 and CP = 7 Btu/lb-mol.F.
Independent of paths!

Two-step process:

(1) cooled at constant volume to the final pressure;

(2) heated at constant pressure to the final temperature.

T1 = 40 + 459.67 = 499.67 R

T2 = 140 + 459.67 = 599.67 R

Constant volume

T = T1

P1
= 49.97 R
P2

Constant pressure

V2 = V1

P1T2
= 437.93 ft 3
P2T1

U = CV T = 2248.5 Btu

H = C P T = 3847.9 Btu

H = U + ( PV ) = 3141 .6 Btu

U = H PV = 2756.2 Btu

Intermediate state

H = H 1 + H 2 = 507.7 Btu
U = U 1 + U 2 = 706.3 Btu

m& 1

m& 3

Open systems
m& 2

Mass balance for open systems:

dmcv
= ( m& ) fs = ( uA) fs
dt

(m& ) fs = m& 3 m& 1 m& 2

energy balance for open systems:

d ( mU ) cv
1

= U + u 2 + zg m& + Q& + work rate
dt
2
fs

PV work + shaft work + ... etc.

[( PV ) m& ] fs + W&

d ( mU ) cv
1

= U + u 2 + zg m& + Q& [( PV )m& ] fs + W&
2
dt
fs


d ( mU ) cv
1

+ H + u 2 + zg m& = Q& + W&
dt
2
fs

d ( mU ) cv
+ (Hm& ) fs = Q& + W&
dt

An evacuated tank is filled with gas from a constant-pressure line. What is the
relation between the enthalpy of the gas in the entrance line and the internal energy
of the gas in the tank? Neglect heat transfer between the gas and the tank.
d ( mU ) cv
+ (Hm& ) fs = Q& + W&
dt

No expansion work
No stirring work
No shaft work

d ( mU ) cv
+ (Hm& ) fs = 0
dt
dmcv
= (m& ) fs
dt

(mU ) cv + (H )mcv = 0
( m2U 2 ) (m1U 1 ) + H (m2 m1 ) = 0

U 2 = H

d ( mU ) cv
dm
+ (H ) cv = 0
dt
dt

An insulated, electrically heated tank for hot water contains 190 kg of liquid water
at 60 C when a power outage occurs. If water is withdrawn from the tank at a
steady rate of 0.2 kg/s, how long will it take for the temperature of the water in the
tank to drop from 60 to 35 C? Assume that cold water enters the tank at 10 C and
that heat losses from the tank are negligible. For liquid water let Cv = Cp = C, independent
of T and P.

d ( mU ) cv
+ (Hm& ) fs = Q& + W&
dt

dU
+ m& (H H 1 ) = 0
dt

dU
dT
=C
dt
dt

dt =

(H H1 ) = C (T T1 )
m dT
m& T T1

m T T1

t = ln
m& T0 T1

t=

190 35 10
ln
= 658.5 s
0.2 60 10

Air at 1 bar and 25 C enters a compressor at low velocity, discharge at 3 bar, and
enters a nozzle in which it expands to a final velocity of 600 m/s at the initial
conditions of pressure and temperature. If the work of compression is 240 kJ/kg of
air, how much heat must be removed during the compression?

d ( mU ) cv
1

+ H + u 2 + zg m& = Q& + W&
dt
2
fs

Steady state flow process

Return to initial pressure and temperature, no enthalpy change
No potential energy change
Initial kinetic energy is negligible

u 22
= Q + Ws
2
Q=

1
(600 )2 240 = 60 kJ / kg
2

Heat must be removed in the amount of 60 kJ for each kilogram of air compressed.

Water at 200 F is pumped from a storage tank at the rate of 50 gal/min. The motor
for the pump supplies work at the rate of 2 (hp). The water goes through a heat
exchanger, giving up heat at the rate of 40000 Btu/min. and is delivered to a second
storage tank at an elevation 50 ft above the first tank. What is the temperature of
the water delivered to the second tank?

d ( mU ) cv
1

+ H + u 2 + zg m& = Q& + W&
dt
2
fs

Steady state flow process

Kinetic energy is negligible
[(H + zg )m& ] = Q& + W& s

H = Q + Ws

g
z = 99.35 Btu / lbm
gc

From steam table, H1 = 168.09 Btu/lbm

H 2 = H + H 1 = 99.35 + 168.09 = 68.74 Btu / lbm

From steam table

t = 100.74 o F