PHYSICS XII

CHAPTER # 16
FIRST LAW OF THERMODYNAMICS

HEAT: (ENERGY IN TRANSIT)

DEFINITION:
“Amount of thermal energy that transfer from one body to another body, when
they are in thermal contact with each other, because of difference of temperature .

UNITS OF HEAT:

S.I UNIT: S.I unit of Heat is Joule (J)

CGS SYSTEM: calorie (cal) is unit of measurement of heat is CGS system.

One calorie is the amount of heat required to raise the temperature of
one gram of pure water from 14.5˚C to 15.5˚C.
1cal=4.186 J OR 4.2J
BRITISH ENGINEERING SYSTEM (F.P.S SYSTEM):
1BTU ( BRITISH THERMAL UNIT) =1055J
1BTU =251.2 cal

SYSTEM:
A collection of matter with well-defined boundaries is
called system. A boundary is a physical or imaginary separation
between system and its surroundings. The surroundings refer to
everything outside the boundaries of the system.
OPEN SYSTEM:
In an open system, both heat and matter can be
exchanged with the surroundings. For example, a cup of hot
coffee.
CLOSED SYSTEM:
In a closed system, only heat can be exchanged with
the surroundings and matter cannot be exchanged. For
example, a glass of hot water with a lid.
ISOLATED SYSTEM:
In an isolated system, neither heat nor matter can be
exchanged with the surroundings. For example, a thermos flask
with hot or cold water inside.

THERMODYNAMICS:
DEFINITION:
That branch of physics that deals with the transformation of heat energy into
mechanical energy (i-e workdone ) and the Laws that governs there conversion.
“The study of the flow of heat or any other form of energy into or out of a system as
it undergoes a physical or chemical transformation is called Thermodynamics.”

WORK DONE IN THERMODYNAMICS:

Consider an ideal gas enclosed in a cylinder provided with a frictionless, move
able piston of area of cross –section ‘A’. A constant pressure is applied by putting
some weights on it.
Let the initial volume be V1 .and the cylinder is placed on a heat reservoir of high
heat capacity, amount of heat ∆Q flows into the system and the gas expanse by
pushing the piston upward through a displacement ‘∆Y and volume becomes V2.

As 𝑃=F/A
F= 𝑃A
Work done by the gas is ∆ W= force x displacement
∆ W = (𝑃A) x (∆y)
= (𝑃) x (𝐴∆y) (∴A∆Y=∆V)

∆W = P∆V

INTERNAL ENERGY:
Definition:
The sum of the random distribution of kinetic and potential energies within
a system of molecules is called the internal energy of the substance. It is denoted by
“U”.
Unit: Joule

Explanation:
Internal energy of the substance is directly related to its temperature.
Internal energy can be increased by doing work on the system or by adding heat to
the system. It can be decreased by removing heat from the system or work done by
the system without giving heat to the system.
When a gas in a container is heated the gas molecules move faster
increasing their kinetic energy. In a solid where molecules are tightly packed, heating
causes the molecules to vibrate more. In both liquids and solids, molecules have both
kinetic energy and potential energy due to intermolecular forces that keep close them
together. Ideal gas molecules have no intermolecular forces, they only possess kinetic
energy and no potential energy.
The average kinetic energy of molecules of ideal monoatomic gas is
 K.Eavg = 3 kT
2
For “N” molecules, it becomes internal energy of the gas,
U = 3 kTN
2
= 3 kTnNA
2
2
ΔU = 3 nRΔT
2
ΔU ∝ ΔT
It means that change in internal energy ΔU is directly proportional to change in
temperature ΔT. The change in internal energy depends on initial and final states and
not on the path taken between these two states.

FIRST LAW OF THERMODYNAMICS:

Statements:
“The change in internal energy of a system in any process is equal to net heat flow
into the system minus the total work done ‘W’ by the system .“
∆𝑈= ∆𝑄-∆W
OR
∆ 𝑄 = ∆ W + ∆𝑈
1. Total energy in a closed system is constant; i-e the energy is conserved in
any transfer of energy from one form (i-e Heat ) to another(i-e work done)
2. “When heat energy is transformed in to mechanical energy or vice versa , the
total amount of energy of the system remains constant “
Sign Convention:-
We often use these sign conventions:
∆ 𝑄 =positive (when heat enters a system)
∆ 𝑄 = negative (when heat is rejected by a system)
∆ 𝑊 = positive (when work done by a system)
∆ 𝑊 = negative (when work done on the system)
∆ 𝑈 = positive (when internal energy of the system increases)
∆ 𝑈 = negative (when internal energy of the system decreases)

Application of First law Of Thermodynamics

1. ISOBARIC PROCESS:
Definition: A thermodynamic process which takes places at constant pressure is
called isobaric process.
CONDITION FOR PROCESS: To achieve isobaric process, gas is enclosed in a
cylinder fitted with a moveable frictionless piston at the upper end.
EXPLANATION:
Consider a gas as working substance enclosed in a cylinder at volume V1 and
temperature T1.When ∆Q amount of heat is supplied to the system at constant
 pressure then some part of heat is utilized in increasing K.E of molecules of gas
and the reaming part of it is utilized in doing work. Thus the gas will expand and
its final volume becomes V2 at temperature T2.
Now, we find the useful work done by heat during isobaric process.

Let, P is the pressure which is kept constant.

∆Q = heat supplied
∆Y = distance moved by the piston
A = cross-section area of piston.
∆W =Work done by gas

∆W =F . ∆Y
= PA. ∆Y
∆W=P(A∆Y)
since, A∆Y= ∆V
∆W=P∆V

Now, according to 1st law of

thermodynamics ,
∆Q = ∆ 𝑊 + ∆ U

In this case, ∆Q = P∆V + ∆ U

∆Q = P(𝑉2 -𝑉1 ) + ∆ U
Conclusion: In isobaric process, heat
supplied to the system is used to increase
the internal energy and to do work during
expansion.

Graph: The graph of an isobaric process is

a horizontal straight line parallel to x-axis
& it is called an isobar.

2.ISOCHORIC PROCESS:
A thermodynamic process which takes place at constant volume is called
isochoric process.
CONDITION FOR PROCESS:
The piston must be kept fixed so that no volume is changed.
EXPLANATION:
Consider a gas enclosed in a cylinder fitted with a moveable frictionless piston.
When heat is supplied to the cylinder containing gas, the internal energy of the
molecules increases as a result the impact of the molecules with the surface
increases. In order to balance the inter-molecular forces, the external pressure
is increased up to the limit that volume remains constant.
Let V = Constant volume
∆𝑄 = heat supplied
∆ 𝑈= U2 – U1 =change in internal energy
Since volume is constant,
∆V = 0 and ∆ W =0

Now ∆𝑄 = ∆ W +∆ 𝑈
∆𝑄 = 0 + ∆𝑈
∆𝑄 = ∆ 𝑼
GRAPH: The P-V diagram of isochoric process is a vertical straight line parallel to y-
axis called isochor.
Conclusion: P
Thus in isochoric process, heat supplied to the P2 (P2, V)
system is used to increase the internal energy.
P1 (P1, V)

V
3- ISOTHERMAL PROCESS:
A thermodynamic process which takes place at constant temperature is called
isothermal process.
CONDITION FOR PROCESS:
To achieve isothermal process, gas is filled in a cylinder of insulating walls and
conducting base and the cylinder must be placed on heat reservoir of same initial
temperature as that of gas.
EXPLANATION:
Consider a gas enclosed in a cylinder fitted with a moveable frictionless piston.
The cylinder is placed on a heat reservoir at temperature ‘T’.Let P1,V1,T are the initial
parameters of the gas Now the gas is allowed to expand by decreasing pressure to P2
so the volume increases to
V2.Due to expansion,
temperature of the gas falls
down but heat is supplied by
the reservoir through
conducting base until the
temperature maintained to
‘T’.
Let, ∆ Q= heat supplied
T = constant temperature
According to first law of
thermodynamics,
∆𝑄 = ∆ W +∆ 𝑈
But in this case, since
temperature is constant,
Hence, ∆𝑈=0
Then, ∆𝑄 = ∆ W + 0
 ∆𝑄 = ∆ W
Conclusion: This indicates that the heat supplied in isothermal process is used to do
work only. This process is performed slowly because flow of heat requires time.
Conversely, if the gas contracts by increasing load on the piston, the work is done on
the system and some amount of heat leaves the gas
to maintain the temperature. As pressure and
volume are inversely proportional to each other and
temperature is constant, Boyle’s law holds good.

PV = constant

GRAPH: The graph between pressure and volume in

isothermal process is called isotherm.

4. ADIABATIC PROCESS:
The word adiabatic comes from the Greek for “cannot be crossed”.
A thermodynamic process in which no heat enters or leaves the system is called
adiabatic process. This process is performed rapidly.

ADIABATIC EXPANSION:
Consider a gas enclosed in a cylinder is placed on an insulator so, that no heat
can enter or leave the system. Now if pressure of the gas is decreased the volume
increases, temperature and internal energy of the gas decreases. The work is done at
the cost of the internal energy of the gas and the gas cools down.

According to 1st law of thermodynamics:

∆ Q =∆W + ∆ 𝑈
0 = ∆W+ ∆ 𝑈
Since, ∆ Q =0

∆ W =- ∆ 𝑈
CONCLUSION:
In adiabatic expansion the work is done at the cost of internal energy of the
molecules so the internal energy decreases.
ADIABATIC COMPRESSION:
In this the gas is compressed suddenly by increasing the load on the piston.
The volume of the gas decreases, temperature and the internal energy of the gas
increases. As no heat enters or leaves the system
∆ Q =0
∆ 𝑈 =- ∆ W
Work is done on the system and the internal energy of the gas increases. As pressure
and volume are inversely proportional and temperature is not constant the equation
holds is
PVɣ = CONSTANT

GRAPHICALLY: The graph between pressure

and volume for adiabatic process is called
adiabat. It is steeper than isotherm.

Conclusion:
This shows that in adiabatic process work done
by the gas is equal to its own loss of internal
energy.

HEAT CAPACITY:
“The amount of heat required to raise the temperature of a body by 10C is called as heat
capacity”
FORMULA:
∆𝑄
C= ∆𝑇

SI UNIT:
The SI unit of heat capacity is J/K.

SPECIFIC HEAT CAPACITY:

“The quantity of heat required to raise temperature of unit mass of a substance by unit
degree is called as specific heat capacity “
FORMULA:
∆𝑄
c=
𝑚∆𝑇
Where
c is specific heat capacity
ΔQ is amount of heat
m is the mass of a substance
ΔT is the change in temperature
SI UNIT:
The SI unit of specific heat capacity is J/Kg.K or J/kg.˚C
MOLAR SPECIFIC HEAT CAPACITY:
“Amount of heat required to raise the temperature of one mole of a substance by unit
degree is called as molar specific heat”
FORMULA:
∆𝑄
Cn=
𝑛∆𝑇
Where
C is molar specific heat capacity
ΔQ is amount of heat
n is the number of moles of a substance
ΔT is the change in temperature

SI UNIT:
The SI unit of molar specific heat is J/mole K or J/mole 0C

MOLAR SPECFIC HEAT AT CONSTANT PRESSURE:

DEFINITION:
Amount of heat required to raise the temperature of one mole of a gas through
one degree (1K or1℃) at constant pressure is called molar specific heat at constant
pressure(𝑪𝒑 ).
MATHEMATICALLY:
⬚ ∆𝑸𝒑
𝑪𝒑 = 𝒏∆𝑻
Where, ∆𝑸𝒑 is amount of heat supplied at constant pressure.

SI UNIT: J/mole K

MOLAR SPECFIC HEAT AT CONSTANT VOLUME:

DEFINITION:
Amount of heat required to raise the temperature of one mole of a gas through
one degree (1K or1℃) at constant volume is called molar specific heat at constant
volume(𝑪𝒗 ).
MATHEMATICALLY:
∆𝑸𝒗
𝑪𝒗 =
𝒏∆𝑻
Where, ∆𝑸 is amount of heat supplied at constant volume.

SI UNIT: J/mole K

RELATIONSHIP BETWEEN MOLAR SPECFIC HEAT AT CONSTANT

PRESSURE AND MOLAR SPECFIC HEAT AT CONSTANT VOLUME:
PROVE THAT: Cp - CV = R
 Consider two ideal gas isotherms at T1 andT2 i.e (T2 > T1).As we know that the internal
energy of an ideal gas depends upon the temperature. Hence each isotherm represents
constant internal energy. If the gas is heated from T1 to T2 along the path (a c) its volume
will remain constant. Similarly If the gas is heated from T1 to T2 along the path (a b) its
pressure will remain constant. Since the change in internal energy is independent of path.
Therefore, for all paths connecting the two isotherms the change in internal has the same
value, because all paths correspond to the same change in temperature.
∆𝑈𝑎𝑏 = ∆𝑈𝑎𝑐 (1)

Let, n =no of moles of a gas

∆ T = change in temperature
∆ Q = amount of heat supplied

The temperature of the gas can be changed in two different ways i-e, at constant pressure
and at constant volume.

1. CONSTANT PRESSURE PATH:(a b)

The heat transferred (∆Q) in constant pressure process can be written as

∆𝑄𝑝
∆𝑄𝑝 =n 𝐶𝑝 ∆T ∴ 𝐶𝑝 =
n∆T

From first law of thermodynamics, ∆U = ∆𝑄𝑝 - ∆W ∆W = P ∆V

∆𝑈𝑎𝑏 = n 𝐶𝑝 ∆T - P ∆V (2)
From general gas equation, PV= nRT
For initial state of gas, PV1 = nRT1
For final state of gas, PV2 = nRT2
By subtracting the above equations,
PV2 - PV1 = nRT2 - nRT1
P(V2 – V1)= nR(T2 - T1)
P∆V = n R ∆T

Substituting P∆V in equation (2) we get,

 ∆𝑈𝑎𝑏 =n 𝐶𝑝 ∆T- n R ∆T (3)

CONSTANT VOLUME PATH: (a c)

The heat supply in constant volume process can be written as,
∆𝑄𝑣 =n 𝐶𝑣 ∆T
∆𝑄𝑣
∴ 𝐶𝑣 =
n∆T
From first law of thermodynamics, ∆U = ∆𝑄𝑣 - ∆W
Since, the volume is constant (∆W = 0),
∆U = ∆𝑄𝑣
∆𝑈𝑎𝑐 = n 𝐶𝑣 ∆T (4)

Putting the value of ∆𝑈𝑎𝑏 𝑎𝑛𝑑 ∆𝑈𝑎𝑐 in eq (1),

n 𝐶𝑝 ∆T- n R ∆T= n 𝐶𝑣 ∆T
n 𝑪𝒑 ∆T- n 𝐶𝑣 ∆T = n R ∆T

n ∆T(𝐶𝑝 -𝐶𝑣 ) = n ∆T R

𝑪𝒑 - 𝑪𝒗 =𝐑
Hence the above equation shows that CP > CV and the difference of molar specific heat
at constant pressure (CP) and molar specific heat at constant volume (CV) is equal to
universal gas constant.
TABLE OF CV & Cp FOR DIFFERENT TYPES OF GASES:
Nature of gases CV CP γ = CP/ CV
Monoatomic gas
3 5 5
2
𝑅 𝑅 =1.67
2 3

Diatomic gas
5 7 7
𝑅 𝑅 =1.4
2 2 5

Polyatomic gas 3𝑅 4𝑅
4
=1.33
3
NOTE: For all gases molar specific heat at constant pressure (CP) is always greater
then molar specific heat at constant volume(CV).

Q) Why is CP greater than CV ?

When ‘n’ moles of ideal gas are heated at constant pressure then the amount of heat
∆𝑄𝑝 supplied to the system of gas is subdivided into two parts some amount of it is used to
increase the kinetic energy of molecules of gas whereas rest of the heat does some useful
work against the constant pressure Since only a part of supplied heat is utilized in increasing
internal energy of this system therefore we must needed greater amount of heat to raise the
temperature of gas up to a constant value of ∆𝑇.Now consider the same system of gas at
constant volume when the amount of heat is supplied to a system of gas at constant volume
it is totally utilized in increasing internal energy of the system and hence much lesser amount
of heat is needed it to raise the temperature of gas up to same temperature difference ∆𝑇.
For n moles of ideal gas which are heated up to temperature difference ∆𝑇
As we analyze we may write mathematically as ,

∆𝑄𝑝 >∆𝑄𝑣
n 𝐶𝑝 ∆ T > n𝐶𝑣 ∆ T
𝑪𝒑 > 𝑪𝒗
It means that the Molar specific heat at constant pressure (CP) is always greater than
Molar specific heat at constant volume (CV)

MOLAR SPECFIC HEAT CAPACITIES OF MONO-ATOMIC GAS:

3 𝟓
DERIVE: 𝐂𝐯 = R & 𝑪𝒑 = 𝐑
2 𝟐
Consider ‘ n’ moles of mono atomic gas heated at constant volume, the amount of heat
supplied is completely used used to increase the internal energy of the gas which increases
the translational K.E of ‘N’ number of molecule.

∆𝐐𝐯 = ∆𝑈

∆𝐐𝐯 = 𝐍(∆ 𝐾. 𝐸)

𝟑
but, ∆ 𝑲. 𝑬 = 𝑲 ∆𝑻
𝟐

𝑹
∆𝐐𝐯 = 𝑵(𝟑𝟐 𝑲 ∆𝑻) ∴ 𝐾=𝑵
𝑨

𝟑 𝑹
∆𝐐𝐯 = 𝑛𝑵𝑨 ( 𝟐 × 𝑵𝑨
× ∆𝑻) ∴ N= 𝒏𝑵𝑨

∆𝐐𝐯 𝟑
= 𝑹
𝒏∆𝑻 𝟐

𝟑
𝐂𝐯 = 𝟐
𝐑 ∆𝐐𝐯
∴ 𝑪𝒗 =
𝒏∆𝑻
We know that, 𝑪𝒑 - 𝑪𝒗 = 𝐑

𝟑
but, 𝐂𝐯 = 𝐑,
𝟐

∴ 𝑪𝒑 - 𝟑𝟐 𝐑 = 𝐑
𝟑
𝑪𝒑 = 𝐑 + 𝐑
𝟐
𝟓
𝑪𝒑 = 𝐑
𝟐