Advanced Chemical Engineering

Thermodynamics (ChEg6121)

MSc I Year – Sem 1 (2020-21)

Chapter 1
Review of Basic Thermodynamics

Dr. Prasanna Rani. R

Department of Chemical Engineering

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 Thermodynamics and Energy

 Thermodynamics is the science of energy.

 Energy is the ability to cause changes/ ability to do work.

 The name thermodynamics is derived from the Greek words

therme (heat) and dynamis (power), which is most descriptive of
the early efforts to convert heat into power.
 Thermodynamics is broadly interpreted to include all aspects of
energy and energy transformations, including power generation,
refrigeration, and relationships among the properties of matter.

2
 Conservation of energy principle:
 One of the most fundamental laws of
nature

 It states that during an interaction,

energy can change from one form to
another but the total amount of energy
remains constant.
Energy cannot be created nor destroyed
but can be transferred from one form to
another.

Figure 1. Change of PE to KE

3
Application Areas of Thermodynamics

 Thermodynamics is commonly encountered in many

engineering systems and other aspects of life activities that
involve energy and energy interactions.
 Areas that use the thermodynamics principle include:
 Chemical process (Separation, reaction , Heat and mass
transfer…..)
 Air-conditioning systems
 Refrigeration systems
 Power Generation
 Renewable energy applications (e.g. solar collectors, solar
cells) and etc…..

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Systems and Control Volumes
 System: A quantity of matter or a region in space chosen for
study. E.g. reaction vessel, distillation column, or a heat
engine.
 Surroundings: The mass or region outside the system,
separated from the system by boundaries.
 Boundary: The real or imaginary surface that separates the
system from its surroundings.
 The boundary of a system can be fixed or movable.
 Systems may be considered to be closed or open.

Figure 2. System, surroundings, and boundary

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 Closed system (Control mass)
 A fixed amount of mass, and no mass can cross its boundary but
energy can cross its boundary.
 If, as a special case, even energy is not allowed to cross the
boundary, that system is called an isolated system.

(a) Fixed Boundary (b) Moving Boundary

Figure 3. Closed System

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 Open system (Control Volume)
 It usually encloses a device that involves mass flow such as a
chemical reactor, compressor, turbine, or nozzle.
 Both mass and energy can cross the boundary of a control
volume.
 The boundaries of a control volume is called Control surface, It
can be real or imaginary.

feed

Reactor

Product

Figure 4. Open System

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 Properties of a System
 Property: Any characteristic of a system; E.g. pressure P, temperature T,
volume V, and mass m.
 Properties are considered to be either
intensive or extensive.
 Intensive properties: Those that are
independent of the mass of a system, such
as temperature, pressure, and density.
 Extensive properties: whose values depend
on the size or extent of the system. (total
mass, total volume, total momentum)
 Specific properties: Extensive properties per
unit mass. (specific volume v=V/m, specific
total energy e=E/m)

Figure 5. Criterion to differentiate intensive and

extensive properties
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 Equilibrium State and the Phase rule
 Thermodynamics deals with equilibrium states.
 Equilibrium: A state of balance or a state of rest.
 In an equilibrium state there are no unbalanced potentials (or
driving forces) within the system.
 The properties are uniform throughout and they do not vary with
time.

Equilibrium and steady-state are different.

Steady State: A system which is interacting with the surroundings is

said to have attained a steady-state condition when the properties at a
specified location in the system do not vary with time.
The properties at different points in the system can be different.

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 Thermal equilibrium: If the temperature is the same throughout the
entire system – no heat exchange occurs within the system.
 Mechanical equilibrium: If there is no change in pressure at any point
of the system with time.

Even under the conditions of uniform temperature and pressure, transfer

of mass may occur between various phases of a system, or chemical
reaction may occur between the various components in the system.
A system in thermodynamic equilibrium, in addition to the absence of
heat and work exchange there would be no mass transfer between the
phases, no diffusion within the phase and no chemical reaction between
the constituents.
 Phase equilibrium: If a system involves two phases and when the
mass of each phase reaches an equilibrium level and stays there.
 Chemical equilibrium: If the chemical composition of a system does
not change with time, that is, no chemical reactions occur.
 A system will not be in equilibrium unless all relevant equilibrium
criteria are satisfied. 10
The Phase rule
 The state of an equilibrium system consisting of a pure fluid is
uniquely determined by specifying any two intensive variables.
 The number of independent variables necessary to define the
state of equilibrium is known as degrees of freedom. It will be
different for different equilibrium states.
 Gibbs phase rule:- gives relation between the number of degrees
of freedom (F), number of distinct chemical species in the system
(c) and the number of phases present at equilibrium (P).
F=C–P+2

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The zeroth law of Thermodynamics
 If two bodies are in thermal equilibrium with a third body, they are
also in thermal equilibrium with each other.
 By replacing the third body with a thermometer, the zeroth law can
be restated as two bodies are in thermal equilibrium if both have the
same temperature reading even if they are not in contact.

Figure 6. Two bodies reaching thermal equilibrium after being brought into contact in an isolated enclosure.

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Process and Cycle
 Process: Any change that a system
undergoes from one equilibrium state to
another.
 Can be visualized using Process
diagrams plotted by employing
thermodynamic properties as
coordinates.
 Some common properties that are used
as coordinates are temperature T,
pressure P, and volume V (or specific
volume v).
 Cycle: A system is said to have undergone a
cycle if it returns to its initial state at the
end of the process.
Figure 7. The P-V diagram of a compression
process.

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 The prefix iso- is often used to designate a process for
which a particular property remains constant.

 Isothermal process: A process during which the

temperature T remains constant.

 Isobaric process: A process during which the pressure

P remains constant.

 Isochoric (or isometric) process: A process during

which the specific volume v remains constant.

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The Steady-Flow Process
 The term steady implies no change with
time. The opposite of steady is unsteady,
or transient.

 A large number of engineering devices

operate for long periods of time under
the same conditions, and they are Figure 8. Steady state processes
classified as steady-flow devices.

 Steady-flow process: A process during which a fluid flows

through a control volume steadily.
 Steady-flow conditions can be closely approximated by devices
that are intended for continuous operation such as turbines,
pumps, boilers, condensers, and heat exchangers or power plants
or refrigeration systems.

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The First Law of Thermodynamics
• The first law of thermodynamics is a statement of the conservation of
energy.
• The first law of thermodynamics states that energy can neither be
created nor destroyed during a process; it can only change from one
form to another.
• Conservation of energy (The first law of thermodynamics) can be
expressed :

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Closed system

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The First Law of Thermodynamics for flow process:
Consider a fluid flowing through from section 1 to section 2:

Energy balance for unit mass of the fluid is:

U1 + gZ1 + P1V1 +1/2 u12 + Q – Ws = U2 + gZ2 + P2V2 +1/2 u22

ΔU + Δ PV + g ΔZ + ½ Δu2 = Q – Ws ΔH + g ΔZ + ½ Δu2 = Q – Ws
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The second law of thermodynamics

 In a system, a process that occurs will tend

to increase the total entropy of the
universe.
 The Second Law of Thermodynamics
(Kelvin–Planck Statement) states that :
 Heat generally cannot flow
spontaneously from a material at lower
temperature to a material at higher
temperature (Clausius)
 It is impossible to convert heat
completely into work in a cyclic
process (Kelvin–Planck )

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The quantitative definition of entropy requires the following
specifications:
1. The amount of heat transferred
2. The temperature level at which the transfer occurs
3. The nature of the process, whether reversible or irreversible

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Areas of Application
 The second law may be used to identify the direction of
processes.
 The second law also asserts that energy has quality as well as
quantity.
 The first law is concerned with the quantity of energy and the
transformations of energy from one form to another with no regard
to its quality. The second law provides the necessary means to
determine the quality as well as the degree of degradation of
energy during a process.
 The second law of thermodynamics is also used in determining
the theoretical limits for the performance of commonly used
engineering systems, such as heat engines and refrigerators, as
well as predicting the degree of completion of chemical reactions.

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Heat engines
• The devices that convert heat to
work.
 They receive heat from a high-
temperature source (solar energy, oil
furnace, nuclear reactor, etc.).
 They convert part of this heat to work
(usually in the form of a rotating
shaft.)
 They reject the remaining waste heat
to a low-temperature sink (the
atmosphere, rivers, etc.).
 They operate on a cycle.

• Heat engines and other cyclic devices usually involve a fluid to and
from which heat is transferred while undergoing a cycle. This fluid is
called the working fluid.
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Steam Power Plant-Rankine Cycle

 Part of the work output of a heat

engine is consumed internally to
maintain continuous operation (e.g.
Pump Power supply in Rankine
cycle) , hence:

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Ideal Rankine Cycles

Process 1-2: Isentropic compression in a pump

Process 2-3: constant-pressure heat addition in a boiler
Process 3-4: Isentropic expansion in a turbine
Process 4-1: constant-pressure heat rejection in a condenser
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Water enters the pump at state 1 as saturated liquid (quality, x = 0) and is
compressed isentropically to the operating pressure of the boiler. The
water temperature increases somewhat during this isentropic
compression process due to a slight decrease in the specific volume of
water.
Water enters the boiler as a compressed liquid at state 2 and leaves as a
superheated vapor (quality, x = 1) at state 3. The boiler is basically a
large heat exchanger where the heat originating from combustion gases,
nuclear reactors, or other sources is transferred to the water essentially at
constant pressure.

The superheated vapor at state 3 enters the turbine, where it expands

isentropically and produces work by rotating the shaft connected to an
electric generator. The pressure and the temperature of steam drop
during this process to the values at state 4, where steam enters the
condenser. At this state, steam is usually a saturated liquid–vapor
mixture with a high quality.
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Steam is condensed at constant pressure in the condenser, which is
basically a large heat exchanger, by rejecting heat to a cooling
medium such as a lake, a river, or the atmosphere. Steam leaves the
condenser as saturated liquid and enters the pump, completing the
cycle. In areas where water is precious, the power plants are cooled
by air instead of water.

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Energy Analysis of the Ideal Rankine Cycle

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Example 10.3 – Boles and Cengel

• Consider a steam power plant operating on the Ideal Rankine Cycle.

Steam enters the turbine at 3Mpa and 350 oC and is condensed in the
condenser at a pressure of 10 kPa. Determine (a) the thermal
efficiency of this power plant . (b) the thermal efficiency if steam is
superheated to 600 oC Instead of 350 o C. and (c) the thermal
efficiency If the boiler pressure is raised to 15 MPa while the turbine
Inlet temperature is maintained at 600 o C.
29
Problem Solving using EES tool (Engineering Equation Solver)
 EES is a program that solves systems of linear or nonlinear algebraic
or differential equations numerically.
 It has a large library of built-in thermodynamic property functions as
well as mathematical functions, and allows the user to supply
additional property data.
 Unlike some software packages, EES does not solve engineering
problems; it only solves the equations supplied by the user. Therefore,
the user must understand the problem and formulate it by applying
any relevant physical laws and relations.
 EES saves the user considerable time and effort by simply solving the
resulting mathematical equations. This makes it possible to attempt
significant engineering problems not suitable for hand calculations,
and to conduct parametric studies quickly and conveniently.
 EES is a very powerful yet intuitive program that is very easy to use.

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Exergy / Availability: A Measure of Work Potential

 Exergy (also called Availability or Work Potential): the

maximum useful work that can be obtained from a system at a
given state in a given environment; in other words, the most
work you can get out of a system

 Surroundings: outside the system boundaries.

 Environment: the area of the surroundings not affected by the
process at any point (For example, if you have a hot turbine, the
air next to the turbine is warm. The environment is the area of
the surroundings far enough away that the temperature isn’t
affected.)
 Dead State: when a system is in thermodynamic equilibrium
with the environment, denoted by a subscript zero; at this point
no more work can be done.

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 At the dead state
1. A system is at the same temperature and pressure of its
surroundings (in thermal and mechanical equilibrium).
2. There are no unbalanced magnetic, electrical and surface
tension effects between the system and its surroundings
(mechanical equilibrium).
3. It has zero kinetic and potential energy relative to its
surroundings (zero velocity and zero elevation above a
reference level).
4. It does not react with the surroundings (chemically inert).

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 Work = f (initial state, process path, final state)
• Hence to maximize the work output
The process to be executed is reversible.
The final state is a dead state.
 A system will deliver the maximum possible work as it
undergoes a reversible process from the specified initial state to
the state of its surroundings, i.e., the dead state.
 Exergy does not represent the amount of work that a work-
producing device will actually deliver upon installation. Rather,
it represents the upper limit on the amount of work a device can
deliver without violating any thermodynamic laws.
 The difference between exergy and the actual work delivered by
a device represents the room Engineers have for improvement.
 Exergy of a system at a specified state depends on the
conditions of the surroundings (the dead state) as well as the
properties of the system.
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Why we study exergy?

• In the last several decades, exergy analysis has begun to be

used for system optimization.
• By analyzing the exergy destroyed by each component in
a process, we can see where we should be focusing our
efforts to improve system efficiency.
• It can also be used to compare components or systems to
help make informed design decisions.

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Exergy Transfer from a Furnace
Example: Consider a large furnace that can transfer heat at a
temperature of 1111 K at a steady rate of 3165 kJ/s. Determine
the rate of exergy flow associated with this heat transfer.
Assume an environment temperature of 298 K.
Solution: The furnace in this example can be modeled as a heat
reservoir that supplies heat indefinitely at a constant
temperature. The exergy of this heat energy is its useful work
potential, that is, the maximum possible amount of work that
can be extracted from it. This corresponds to the amount of
work that a reversible heat engine operating between the
furnace and the environment can produce.

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The thermal efficiency of this reversible heat engine is

That is, a heat engine can convert, at best, 73.2 percent of the heat
received from this furnace to work. Thus, the exergy of this furnace is
equivalent to the power produced by the reversible heat engine:

Discussion Notice that 26.8 percent of the heat transferred from the
furnace is not available for doing work. The portion of energy that
cannot be converted to work is called unavailable energy. Unavailable
energy is simply the difference between the total energy of a system at a
specified state and the exergy of that energy.

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Reversible work and irreversibility
 The property exergy serves as a valuable tool in determining the
quality of energy and comparing the work potentials of different
energy sources or systems.
 The evaluation of exergy alone, however, is not sufficient for
studying engineering devices operating between two fixed states.
This is because when evaluating exergy, the final state is always
assumed to be the dead state, which is hardly ever the case for actual
engineering systems.
 The isentropic efficiencies are also of limited use because the exit
state of the model (isentropic) process is not the same as the actual
exit state and it is limited to adiabatic processes.
 In this section, we describe two quantities that are related to the
actual initial and final states of processes and serve as valuable tools
in the thermodynamic analysis of components or systems. These two
quantities are the reversible work and irreversibility (or exergy
destruction).

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Reversible Work
• Wrev (reversible work): the maximum amount of useful work that
can be produced (or the minimum work that needs to be supplied)
as a system undergoes a process between the given initial and final
states.
• This is the useful work output (or input) obtained (or expended)
when the process between the initial and final states is executed in
a totally reversible manner.
• When the final state is the dead state, the reversible work equals
exergy

Wu: useful work; the amount of work done that can

actually be used for something desirable
Wu=W-Wsurr where W=actual work done

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Irreversibility, I
• Any difference between the reversible work Wrev and the useful
work Wu is due to the irreversibilities present during the process, and
this difference is called irreversibility I.
• The irreversibility is equivalent to the exergy destroyed. It
represents the energy that could have been converted into work but
was instead wasted.
 To have high system efficiency, we want ‘I’ to be as small as
possible.
(work output device, like a turbine)

or

(work input device, like a pump)

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 For a totally reversible process, the actual and reversible work
terms are identical, and thus the irreversibility is zero. This is
expected since totally reversible processes generate no
entropy.
 Irreversibility is a positive quantity for all actual (irreversible)
processes since Wrev ≥ Wu for work producing devices and
Wrev ≤ Wu for work-consuming devices.

 Irreversibility can be viewed as the wasted work potential or

the lost opportunity to do work. It represents the energy that
could have been converted to work but was not.
 The smaller the irreversibility associated with a process, the
greater the work that is produced (or the smaller the work that
is consumed).
 The performance of a system can be improved by minimizing
the irreversibility associated with it.
40
40
Processes and irreversibility

• Expanding closed system • constant-volume systems

41
Revised efficiency definition

 The second two are defined for work delivering devices

Wnet
Thermal  th 
Qin
Wactual
Isentropic s 
Wisentropic
Wu
2 nd
Law  II 
Wrev

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Revised efficiency definition

• The second law efficiency for heat engines can also be expressed as :

• The ηth,rev can be calculated using the numerical values of the hot and
cold reservoir temperature values :

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Second law efficiency and system dependence

Second-law efficiency:

 engine B is performing poorly

relative to engine A!!!
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Thus, in general second-law The second-law efficiency is
efficiency for any process: intended to serve as a measure
of approximation to reversible
operation, and thus its value
should range from zero in the
worst case (complete destruction
of exergy) to one in the best case
 Second-law efficiency of all reversible (no destruction of exergy).
devices is 100 percent.
 The second-law efficiency of naturally
occurring processes is zero if none of
the work potential is recovered.
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Determination of Exergy change of a system

Exergy of a closed system…….

 To derive an expression for exergy

change of a closed system, we
consider a piston-cylinder assembly.
 The system undergoes a differential
change of state.
 Heat transfer from the system occurs
through a reversible heat engine (to
avoid any irreversibilities).
 The total work done = Work done
(PdV) + the work done by the
reversible heat engine.
46
From the first law of thermodynamics

47
Integrating from the given state to dead state

48
• Exergy of a closed system, per unit mass φ, can be expressed as :
• (For system with kinetic and potential energies) 2
V
   u  uo   Po  v  vo   To  s  so    gZ
2
• This gives us the maximum work we could possibly get out of a system.
• Usually we will be more interested in the change in exergy from the
beginning to end of a process (i.e. Δφ)
• For single mass stream:

• For multiple streams

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Exergy of a flow system

Exergy change of a flow system consists enthalpy , ( h= u + PV )

The above equation is known as the flow exergy, Ѱ, or ѱ (per unit mass)

50
Exergy of a flow system

Hence the flow exergy change can be expressed as :

The corresponding flow exergy change per unit mass will be:

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Practice Problems:

1. Examples 4.1 to 4.7

2. Examples 6.1 to 6.6
3. Examples 7.1 to 7.5
4. Examples 8.3, 8.4, 8.7, 8.8

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 Fundamental property relations

Some thermodynamic properties can be measured directly, but

many others cannot. Therefore, it is necessary to develop some
relations between these two groups so that the properties that
cannot be measured directly can be evaluated. The derivations are
based on the fact that properties are point functions, and the state
of a simple, compressible system is completely specified by any
two independent, intensive properties.

53
Property relations for homogeneous phases:
 Primary properties: P, V, T, S (pressure, specific volume,
temperature, entropy)
 Derived properties: U, H, A, G (internal energy, enthalpy,
Helmholtz energy, Gibbs free energy)

The four quantities U, H, A, G are called thermodynamic potentials

and are useful in the chemical thermodynamics of reactions and non-
cyclic processes.
Obtaining the differential equations for these four properties as
functions of primary properties by applying the 1st and 2nd laws of
thermodynamics are called as fundamental property relations.
54
Internal Energy (U): energy required to create a system in the absence of
changes in temperature or volume

The 1st law for a closed system gives: dU  dQ  dW ……….. 1.A.1

For a reversible process,

dU  dQrev  dWrev ……….. 1.A.2

where,
dWrev   PdV
dQrev  TdS ……….. 1.A.3

Substituting Eq. 1.A.3 in Eq.1.A.2, we get,

dU  TdS  PdV ……….. 1.A.4

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Enthalpy (H):
The relation between enthalpy and internal energy is:
H  U  PV ……….. 1. A.5

Taking the differential, we get,

dH  dU  d (PV ) ……….. 1. A.6

substitute Eq. 1.A.4 for dU, and expand the differential d(PV),

dH  TdS  PdV  PdV  VdP

we get, dH  TdS  VdP ……….. 1. A.7

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Helmholtz energy (A): measure of the amount of energy you have to put in to
create a system once the spontaneous energy transfer to the sytem from the
environment is accounted for

Helmholtz energy can be written as:

A  U  TS ……….. 1. A.8

Taking the differential, we get,

dA  dU  d (TS ) ……….. 1. A.9

substitute Eq. 1.A.4 for dU, and expand the differential d(TS),

dA  TdS  PdV  TdS  SdT

we get, dA  PdV  SdT ……….. 1. A.10

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Gibbs Free energy (G): The net energy contribution for a system created in
environment temperature T from a negligible initial volume

Gibbs free energy can be written as:

G  H  TS ……….. 1. A.11

Taking the differential, we get,

dG  dH  d (TS ) ……….. 1. A.12

substitute Eq. 1.A.7 for dH, and expand the differential d(TS),

dA  TdS  VdP  TdS  SdT

we get, dG  VdP  SdT ……….. 1. A.13

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Therefore we have:

dU  TdS  PdV
U  Q W
H  U  PV dH  TdS  VdP
A  U  TS dA  PdV  SdT
G  H  TS
dG  VdP  SdT ……….. 1.A

Eqs. 1.A are called fundamental property

relations

59
Canonical variables: The pair of primary variables in which the
thermodynamic potentials can be expressed in. These are important because
when the thermodynamic potentials are expressed in its primary
variables, all of the thermodynamic properties of the system can be
calculated
Canonical variables

dU  TdS  PdV U  U ( S ,V ) S, V

dH  TdS  VdP H  H ( S , P) S, P

dA  PdV  SdT A  A(T ,V ) T, V

dG  VdP  SdT G  G( P, T ) P, T

60
 Maxwell’s equations
Criteria of exactness:
 Thermodynamic properties are continuous point functions and have
exact differentials.
 A property of a single component system may be mathematically
written as z = z(x,y). Eg., P = P(T,v)…. Pressure is a function of
temperature and specific volume.
 The total differential of z is written as
……….. 1.B.1

……….. 1. B.2

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where,
……….. 1. B.3

Taking the partial derivative of M with respect to y and of N with

respect to x yields,

……….. 1. B.4

Since properties are continuous point functions and have exact

differentials, the following is true;
The criteria of exactness
can be applied to
thermodynamic
properties to derive the
……….. 1.B.5 relation between them.
This relation is called the criteria of exactness.

62
The criteria of exactness can be applied to the fundamental
property relations (Eqs.1.A) to get the Maxwell’s equations.

Using Internal energy equation:

Consider Eq. 1.A.4, dU  TdS  PdV

Comparing Eq. 1.A.4 with Eq. 1.B.2,
dz  Mdx  Ndy
Here, M = T, N = -P, x = S, y = V
Applying the exactness criteria to Eq.1.A.4, we get,

 T   P 
     ……….. 1.B.6
 V  S  S V
63
Using Enthalpy equation:

Consider Eq. 1.A.7, dH  TdS  VdP

Comparing Eq. 1.A.7 with Eq. 1.B.2,

dz  Mdx  Ndy
Here, M = T, N = V, x = S, y = P

Applying the exactness criteria to Eq.1.A.7, we get,

 T   V 
   
 P  S  S  P ……….. 1.B.7

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Using Helmholtz energy Using Gibbs free energy
equation: equation:

Consider Eq. 1.A.10, Consider, Eq. 1.A.13,

dA  PdV  SdT dG  VdP  SdT

Here, M = -P, N = -S, Here, M = V, N = -S,
x = V, y = T x = P, y = T

Applying the exactness Applying the exactness

criteria to Eq.1.A.10, we get, criteria to Eq.1.A.13, we get,

 P   S   V   S 
        
 T V  V T  T  P  P T
……….. 1.B.8 ……….. 1.B.9
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Therefore we have:

 T   P 
    
 V  S  S V
dU  TdS  PdV
 T   V 
dH  TdS  VdP    
 P  S  S  P
dA  PdV  SdT  P   S 
   
dG  VdP  SdT  T V  V T
 V   S  ……….. 1.B
    
 T  P  P T

Eqs. 1.B are called Maxwell’s equations

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Maxwell relations are quite important, for two reasons.
 First, they show us that derivatives of thermodynamic
parameters are not completely independent. This can serve
as a consistency check in both experiments and in pen-and-
paper analysis.
 Second, they provide a method to express derivatives involving
difficult-to-measure quantities in terms of ones that are readily
accessible experimentally
 How does one measure the entropy or chemical potential from
experiments? These kinds of quantities are not usually directly
accessible in the lab.
 What we can measure, typically, are mechanical quantities like
pressure, bulk quantities like volume and density, and
thermal properties like temperature and heat flow
 Maxwell relations enable us to express experimentally-
inaccessible quantities in terms of the measurable ones just listed

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1. C. Thermodynamic properties as functions
of temperature and pressure
The most useful property relations for the enthalpy and entropy of a
homogeneous phase result when these are expressed as functions of
and P. What we need to know is how H and S vary with temperature
and pressure. In general, H=H(T,P) and S=S(T,P).
Therefore, we can write the full differential equation as,

 H   H 
dH    dT    dP and dS   S  dT   S  dP
 T  P  P T  T  P  P T
The following derivatives has to be evaluated as functions ……….. 1.C.1
of measurable quantities:
 H   S   H   S 
  ,  ,  , 
 T  P  T  P  P T  P T
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Temperature derivatives:
For enthalpy:
We know that the differential of enthalpy at constant pressure is the
‘Heat capacity’, given as:  H 
   Cp ……….. 1.C.2
 T  P

Also, we have, the equation for enthalpy (Eq.1.A.7 ), dH  TdS  VdP

Dividing Eq. 1.A.7 with dT at constant P:
 H   S 
   T   ……….. 1.C.3
 T  P  T  P

Equating Eq.s 1.C.1 and 1.C.2, we get:

 S  Cp
   ……….. 1.C.4
 T  P T
This is the equation for Cp in relation to entropy.
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Pressure derivatives:
For enthalpy:
We have, the equation for enthalpy (Eq.1.A.7) dH  TdS  VdP
Dividing Eq. 1.A.7 with dP at constant T:
 H   S 
   T  V ……….. 1.C.5
 P T  P T
For entropy: pressure derivative of entropy can be obtained directly for
Maxwell’s equation Eq.1.B.9.
 S   V 
     ……….. 1.C.6
 P T  T  P
Substituting Eq.1.C.5 in Eq. 1.C.4, we get:
 H   V 
   V  T   ……….. 1.C.7
 P T  T  P

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Substituting the equations for partial derivatives (Eqs. 1.C.2, 1.C.4, 1.C.6,
1.C.7) in Eqs. 1.C.1, we get:

 H   H   S   S 
dH    dT    dP dS    dT    dP
 T  P  P T  T  P  P T

  V   dT  V 
dH  C p dT  V  T    dP dS  C p   dP
  T  P  T  T  P

……….. 1.C.8 ……….. 1.C.9

The coefficients of dT and dP in above equations can be evaluated from

heat-capacity and PVT data.

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Other useful relations for H and S:
1  V 
We have the volumetric expansivity (β) written as:    
V  T  P
Equations 1.C.6 and 1.C.7 can now be expressed as: ……….. 1.C.10
 S   H 
    V    (1  T )V
 P T  P T
……….. 1.C.11 ……….. 1.C.12

Therefore, Eq.s 1.C.1 now becomes:

dH  C p dT  V (1   T )dP dS  C p
dT
 VdP
T
……….. 1.C.13 ……….. 1.C.14

β and V are weak functions of pressure for liquids, so they can be

assumed constant.

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Internal energy as function of T and V:
Consider internal energy expressed as a function of T and V.
 U   U 
dU    dT    dV ……….. 1.C.15
 T V  V T
Recall the definition of the specific heat at constant volume
 U  ……….. 1.C.16
CV   
 T V
 U 
Then dU becomes dU  CV dT    dV
 V T ……….. 1.C.17

 U 
  should be evaluated in terms of P-V-T data.
 V  T

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Home task:
  P  
Express equation 1.C.17 as dU  CV dT  T    P dV
  T V 
……….. 1.C.18
Hint:
Consider general equation for dU, dU  TdS  PdV
Expand the differential dS as a function of T and V, use Maxwell’s
Equations, and obtain the Eq.1.C.18

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