KYAMBOGO

UNIVERSITY

FACULTY OF SCIENCE
DEPARTMENT OF CHEMISTRY
BACHELOR OF SCINCE IN CHEMICAL
ENGINEERING
CHE: 215 PHYSICAL CHEMISTRY
TASK: GROUP COURSEWORK
GROUP FOUR; Write short notes about state and path functions, the
first and second laws of thermodynamics
LECTURER: MR. GEODFREY MUHWEZI
DATE: 05/10/2016
GROUP MEMBERS:

NAME:

REG NO:

NAME:

REG NO:

1) KINABEYO MOSES

15/U/137/CHD/GV

10) OWINY FRED

14/U/6040/CHD/PD

2) KIREMBEKA JOSEPH

14/U/134/CHD/GV

11) NABAJJA CALEB

14/U/6015/CHD/PD

3) OKUBAL DANIEL

14/U/137/CHD/GV

12) ONGOLE JOSEPH

14/U/6035/CHD/PD

4) GIMEI BENEDICT

14/U/132/CHD/GV

13) OTUKOL BEN

14/U/6039/CHD/PD

5) BARIGYE EDWARD

14/U/130/CHD/GV

14) EKWARA TONNY

14/U/5981/CHD/PD

6) SSENDAGIRE
GRAHAM

14/U/6042/CHD/PD 15) KIWANUKA ECLAS 14/U/13348/CHD/PD

7)OTIM INNOCENT

14/U/6038/CHD/PD 16) MATOVU FRANK

14/U/6081/CHE/PE

8) ODONG LEO CEASAR

14/U/6033/CHD/PD 17) ASEGA ROBERT

14/U/6059/CHE/PE

9) TAREMWA DEUS

14/U/6046/CHD/PD 18) LUWAGA JULIUS

14/U/6076/CHE/PE

STATE AND PATH FUNCTIONS

(i) State functions. State functions or thermodynamic variables are
variables that describe the momentary state of a thermodynamic
system. Irrespective of the path or process taken from initial state to
final state, the total state of such variables is the same. There are
examples of quantities which do not depend on path. Among these
are; temperature, pressure, specific volume, internal energy,
entropy enthalpy etc.
These properties do not depend on the past history of the substance
or on the path it has followed in reaching a given state. They depend
only on the present conditions however reached. The values of state
functions can always be represented as points on the graph, which
suggests the synonymous term point function.
It should be noted that the differential of a state function is spoken
of as an infinitesimal small change in the property, and is not
referred to as a quantity. The integration of such a differential results
in a finite difference between two values of the property for example
du=u 2 u1= U
u2

dp=p 2 p1= p
u1
p2

p1

The important mathematical property of such a differential is that

any correct expression for it in terms of the state variables (P, T etc.)
must be exact.
ii) Path functions
For path functions, the path from an initial state to final state is
crucial. Each part or segment of the path to the final state is
necessary to take into account. Two important examples of path
functions are heat and work. These two functions are dependent on
how the thermodynamic system changes from the initial state to the
final state.
These two functions are introduced by the equation U
which reperesent s the changetheinternal energy of the system
U =q+ w

If all the change of states of system are plotted and all the points
are conned, then the line joining the change of states of the system
is called the path

THE FIRST LAW OF THERMODYNAMICS

This is the law of energy conservation. The change in total energy of
a system is equal and opposite to the change in total energy of
surroundings.
The first law applies to the system and surroundings, considered
together and not, in general, to the system alone .In its most basic form,
the first law may be written:

(Energy of the system)+

(Energy of surroundings) =0

(i)

In the system, energy changes in various forms may occur, e.g.,

changes in internal

energy, Potential and kinetic energy of a system

as a whole, all potential and kinetic energy of some parts of a system.

Likewise, the energy change of the surroundings may consist of increases
or decreases of energy in various forms. Energy is stored in its potential,
kinetic and internal forms. These forms reside with material objects and
exist because of the position, configuration and motion of water. The
transformations of energy from one form to another and the transfer of
energy from place to place often occur through the mechanisms of heat
and work.
If the boundary of a system does not permit the transfer of matter
between the system and its surrounding, the system is said to be closed
and its mass is necessarily constant. For such a system all energy passing
across the boundary between the system and its surrounding is
transferred as heat and work. Thus the total energy change of the

surrounding must be equal to the energy transferred to or from it as heat

and work i.e.

(Energy of surroundings)=QW

The first term of equation (i) may be expanded to show energy

changes in various forms. If the mass of the system is constant and if only
internal, kinetic and potential-energy changes are involved,

(Energy of the system)

= U+ E K + E P

With these substitutions, Equation (i) becomes

U+ E K + E P =QW

(ii)

Where U , E K , an d E P represent changes in internal, kinetic

and potential energy of the system respectively. The signs to be used on
the right hand side of Equation (ii) must now be chosen. The usual
convention is to regard a quantity of heat as positive when it is
transferred to the system from the surroundings. On the other hand, a
quantity of work is usually regarded as negative when it is transferred
from the system to the surroundings. With this understanding, Equation
(ii) becomes
U + E K + E P =Q-W

(For open system)

(iii)

In words, equation (iii) states that the total energy change of the
system is equal to the heat added to the system minus the work done by
the system. This equation applies to the changes which occur in a
constant-mass system over a period of time.
Closed systems often undergo processes that cause no changes in
external potential or kinetic energy, but only changes in internal energy
.For such processes, the first law (Equation iii) reduces to
U=Q-W (For closed system when E K + E P =0) (iv)

Equation (iv) applies to processes involving finite changes in the

system. For differential changes this equation is written:
dU =dQdW

Changes in internal energy

Internal energy is the energy contained within the system, excluding
the kinetic energy of the motion and the potential energy of the
system as whole due to external force fields.
It keeps account of the gains and losses of energy of the system that
are accounted for its internal state.
When matter transfer is prevented by impermeable containing walls,
the system is said to be closed.
Here the first law of thermodynamics states that the increase in
internal energy is equal to the total heat added plus the work done
on the system by its surroundings.
If the containing walls pass neither matter nor energy, the system is
said to be isolated, then its internal energy cannot change. In a
sense, the first law of thermodynamics may be regarded as
establishing the existence of internal energy.
The internal energy is one of the two cardinal state functions of
the state variables of thermodynamics system.
The internal energy of a given state of a system cannot be
directly measured. It is determined through some convenient chain
of thermodynamic operations and thermodynamic processes by
which the given state can be prepared, starting with reference state
which is customarily assigned a reference value for its internal
energy. Such a chain, or path, can be theoretically described by
certain extensive state variables of the system,
U =Q+W

The internal energy U of a given state of the system is

determined relative to that of a standard state of the system; by
accompany a change of state from the reference state to the given
state.
u= Ei
i

Where U denotes the difference between the internal

energy of the given state and that of the reference state.

It is impossible to calculate the total internal energy hence a

convenient null reference point may be chosen for the internal
energy.
The internal energy is an extensive property. It depends on the
size of the system or on the amount of the substance it contain
When a closed system receives energy as heat, this energy
increases the internal energy.
A second mechanism of change of internal energy of closed system
is the doing of work on the system, either in mechanical form by
changing pressure or volume or by perturbation, such as directing
an electric current through the system.
If the system is open, the third mechanism that increase the
internal energy is transfer of matter into system hence for an open
system,
u=Q+W + Umatter

For a totally isolated system, none of the mechanisms can increase

the internal energy hence the change in internal energy of such
system is equal to a constant that is.
U =A constant

For ideal gas system, the internal energy changes may be

described solely by changes in the kinetic energy of the gas
molecules. Kinetic energy is simply the internal energy
Example: If 1200 joules of heat are added to a System in
energy state U1, and the system does 800 joules of work on the
surroundings, what is the:
1. The energy change for the system, Usys?
U = U2 U1 = q + w
U = 1200 J + (-800 J)
U = 400 J
U = + 400 J
2. The energy change of the surroundings,
Usurr?
Usurr = 400 J
3. The energy of the system in the new state U2?
Usys= U2 U1
U2 = U1 + Usys

U2 = + 400J
Application of the first law of thermodynamics to:
Closed system
Work and heat may enter or leave a closed system across its
boundary and may also be stored in the system as internal
energy.
This is a system that allows exchange of heat and work across
the system boundaries but does not allow transfer of matter
across the boundaries.
With matter excluded, the changes in internal energy are due to
heat transfer Q and due to work W. Mass is not exchanged.
Hence change in internal energy will be
given;
u=Q+W

Isolated system
This is a system where there is no exchange of mass or energy
within the system and its boundaries
For a totally isolated system, none of the mechanisms can change
the internal energy hence the change in internal energy of the
system is constant.
u=A constant

Open system
This is a system that allows the exchange of mass and energy
with the surrounding.
If the system is open, the mechanism that increases the
internal energy is transfer of matter into system.
u=Q+W + Umatter

Applications of the first law of thermodynamics to flow systems

Turbines. Turbines are mechanical devices that convert the
energy of the working fluid to shaft work.
Compressors. These use shaft work to pressurize gases
Throttling machine. Throttling devices are constrictions or
orifices which bring about a drop in pressure. They work on an
assumption that inlet enthalpy=out let enthalpy
Pumps. Like compressors, pumps use shaft work to pressurize
the working fluid.
Limitation of the first law of thermodynamics

The first law of thermodynamics does not tell us why a

spontaneous reaction proceeds in one direction. All it says is that in
any transformation, the energy of the universe (the system and the
surroundings taken together) remains the same before and after any
change. What, then, determines the direction of spontaneous
process?

SECOND LAW OF THERMODYNAMICS

The second law is based on the idea that there is a natural tendency
of any system that is not in equilibrium to move in a certain
direction. Eg a leaning brick left to fall on its own, shiny iron sheets
turning rusty etc.
Spontaneous processes
The term spontaneous change refers to a change happening
without any continuing outside influences. (Spontaneous change is a
process that has a natural tendency to occur
All such processes that occur without external input of energy are
called spontaneous processes. The processes that are spontaneous
in one direction are not spontaneous in the other direction.
Examples of spontaneous processes include; ice melting at room
temperature, heat flow from hot to cold region, the rusting of iron
etc. Spontaneity is associated with an increase in the randomness or
disorder of the system. This randomness is expressed by a
thermodynamic property called entropy.
The second law of thermodynamics is an expression of the universal
law of increasing entropy.
The second law of thermodynamics states that in
spontaneous changes, the universe tends towards a state of greater
disorder. Therefore, all physical and chemical changes occur such
that the total entropy of the universe increases,
S universe = increases or S universe>0 The second law of
thermodynamics states that the total entropy of an isolated system
always increases over time, or remains constant in ideal cases
where the system is in a steady state or undergoing a reversible
process.

S universe= Ssystem+ S sorrounding> 0

]

The entropy of an isolated system never spontaneously

decreases. It increases during the course of a spontaneous change.
e.g. as a hot block of metal cools, the entropy increases as energy
spreads into the surrounding.
Sisolated 0

Changes in entropy
Provided that the temperature is constant, the change in the
entropy of a system can be calculated from the following expression:
S=

q rev
T

[ q rev signifies that the energy must be transfered reversibly ]

For a reversible transfer of energy as heat, the temperatures of the
surroundings and the system must be only infinitesimally different.

Example1
Calculate the entropy change for the reaction below at 25 oc given
that the entropies of N2 H2 and NH3 gases are 191.5, 131.0 and
193.0 J/(k-mol) respectively
2NH3 (g) N2 (g) + 3H2 (g)
2NH3 (g) N2 (g) + 3H2 (g)
Srxn = nS

products

mS

reactants

= [(1) (191.5 J/K mol) + (3) (131.0 J/K mol)] - [(2) (193.0 J/K
mol)]
= (584.5 J/K mol - 386 J/K mol)
Srxn = 198.5 J/K mol (Entropy increases)
Entropy Changes in the Surroundings
A decrease in the entropy of the system is outweighed by an
increase in the entropy of the surroundings. The surroundings
function as a heat source or heat sink.
In an exothermic process, the surroundings absorbs the heat
released by the system, and Ssurr increases. qsys < 0; qsurr > 0
and Ssurr > 0

 In an endothermic process, the surroundings provides the heat

absorbed by the system, and Ssurr decreases. qsys > 0; qsurr <
0 and Ssurr < 0
Example 2
a) Calculate the change in entropy in 1.0L of water at 0 o C when it
absorbs 235J of energy from a heater.
b) If the 1.0L of water is at 99oC, what is the change in entropy?
c) Explain any difference in entropy change

Solutions
o
a. 0 C=( 0+273 )=273 K .

H=235 J

S=

q rev H 235 J
=
=
=0.861 J /K
T
T
273 K

o
b. 99 C=( 99+273 )=372 K

S=

q rev H 235 J
=
=
=0.632 J / K
T
T
372 K

c. The change in entropy is smaller for the water at higher

temperatures because the water molecules are already chaotic.
At low temperature, the same amount of heat transferred had a
greater effect on changes in entropy.
From this, we can conclude that;
The disorder of a system is expected to increase when heat is
added because the additional; heat energy increases the thermal
motion of the molecules. (heating increases thermal disorder)
The disorder of the system is also expected to increase when a
given amount of matter spreads into a greater volume or is mixed
with another substance.
Entropy is therefore a measure of the disorder or randomness of a
system
S>0 disorder increases(favours spontaneity)

 S<0 disorder decreases( doesnot favour spontaneity)

Applications of the second law of thermodynamics

The difference in the quality between the two forms of energy;
heat and work is the subject matter of the second law of
thermodynamics. This difference is such that work is readily
transformed into heat energy even to an efficiency of 100% by
elimination of friction and other energy losses whereas no process
can convert heat completely into work. The joules experiment
showed that energy in form of heat cannot be completely
converted to work; however, energy in form of work can be
completely converted to heat energy.
Heat engines
According to Kelvin Planck statement, that is, no heat engine can
produce a net amount of work while exchanging heat with a
single reservoir only, it shows that the second law does not
prohibit the production of work from heat energy but defines the
limit on the fraction of the heat that may be converted to work in
any cyclic process.
A heat engine expresses the efficiency of this transformation.
The heat engine is a thermodynamic system operating in a
thermodynamic cycle to which net heat is transferred and from
which network is delivered.
Heat pump
This is a thermodynamic system operating in a thermodynamic
cycle that removes heat from a low temperature body to a high
temperature body
Refrigerator
A refrigerator is a cyclic device that extracts heat energy from a low
temperature medium but does not transmit it to high temperature
body

Other statements of the second law of thermodynamics

There are some other statements of the second law of
thermodynamics and they include;
Entropy is a property of the state only. Its value for an isolated
system can never decrease
There is a general tendency in nature for energy to pass from
more available to less available
The state of maximum entropy is the most stable state for an
isolated system
It is impossible to transfer heat from a colder system to a
warmer without other simultaneous changes occurring in the
two systems or their environment
In an adiabatic process, the entropy either increases or
remains unchanged.
The entropy of the universe tends to a maximum value,
approaching zero for a reversible process

REFERENCES
Introduction to Chemical Engineering Thermodynamics by J.
Smith
An Engineering Approach to Thermodynamics by Yunus A.
Principles of chemistry by CHAWLA. H.M, P.L.SONI and
M.S.BATRA