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Lecture 2. THE FIRST LAW OF

THERMODYNAMICS
- Internal Energy, Heat, Work
- Specific Heat and Calorimetry.
- Latent Heat.
- The First Law of Thermo-dynamics.
- Investigation of Isotropic Processes by the First Law of Thermodynamics.
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INTERNAL ENERGY & HEAT

Heat (denoted Q) is the transfer of energy across the boundary of a system.

Heat is present when there is a difference in temperature between two systems
in thermal contact.

Internal Energy (denoted U) is all the energy of a system that is associated

with its microscopic components -- atoms and molecules. But not the bulk
motion. It includes:
Kinetic energy
Chemical bonding
Weak bonding (e.g. protein folding)
Nuclear energy
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Work
• Work is done by forces Vf

W = - ò PdV
Vi

Exercise. Calculate the work associated with the expansion of a gas from 46 L to 64 L
at a constant external pressure of 15 atm.
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SPECIFIC HEAT CAPACITY & CALORIMETRY

A calorimeter is a device used to measure changes in thermal energy
or heat transfer. More specifically, it measures calories. A calorie is the amount
of energy required to raise one gram of water by one degree Celsius. As such,
the calorimeter measures the temperature change of a known amount of water
(or other materials).

Q is a heat transfer, m is a mass of substance, c is a specific heat capacity depending

on the material and phase. is the change in temperature. For water: c=4179.6
J/(kg.K).

Exercise. A pot of 10 kg of 15°C water is put on a stove and brought to a boil. How
much heat was needed?

Q=

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PHASE CHANGES & LATENT HEAT

• The conversion of materials from one form to another can
be expected to incorporate the exchange of energy, i.e.
conversion of ice to water for example.

• But there is no change of temperature!!

Q  mL
m – mass of material, L - latent heat of material
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Phase changes
Blue arrows release energy
Red arrows absorb energy
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At constant pressure:
-High temps gases have ideal
behavior
-Colder, volume drops and
forms liquid
-Colder yet, volume drops and
forms solid

Phase changes of the high temperature gas

upon cooling to low temperature
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THE FIRST LAW OF THERMODYNAMICS

The first law of thermodynamics states that when a

system undergoes a change from one state to another, the
U  Q  W
change in its internal energy is

where Q is the energy transferred into the system by heat

and W is the work done on the system.
Although Q and W both depend on the path taken from the
initial state to the final state, the quantity U does not depend
on the path.
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Exercise. While working on an assignment, Frank does 10000 J of work. In the process,
his internal energy decreases by 20000 J. Find W, ΔU, and Q.

W = -10000 J
ΔU = -20000 J
Q = -10000 J
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Convention

Q: heat transferred to the system.

Q’=-Q: heat transferred from the system
Q>0 : the system really receives energy
Q<0, Q’>0: the system releases energy as heat
W: work done on the system.
W’=-W: work done by the system.
W>0: work is really done on the system
W<0,W’>0: work is really done by the system.
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Work done on the system

 
dW  F.d s  P.S.dy   PdV
V2
W    PdV
V1
APPLICATIONS OF THE FIRST LAW OF 12

TD
Isothermal process of an Ideal Gas
T  const  PV  const
1st law of TD : U  Q  W
i
U  nRT  0; Q   W
2
( 2) V2
nRT V2
W    PdV    dV  nRT ln
(1) V1
V V1
V2
Q   W  nRT ln
V1
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Isobaric process P=const

V
P  const :  const
1st Law of TD T
U  Q  W
Work done on the system
W    PdV   PV  nRT
Heat transferred to the Q  U  W
system
i i2
Q  nRT  nRT  n R T
2  2 
C pm
Q  nC p.m T
i2 The molar specific heat
C p.m  R
2 at constant pressure
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Isovolumetric process V=const

P
V  const :  const
T
1st Law of TD U  Q  W

Work done on the system W    PdV  0

i
Heat transferred to the Q  U  nRT  nC v.m T
system 2

The molar specific i

heat at constant C v.m  R
volume 2
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Adiabatic process Q=0

1st Law of TD U  Q  W

Q0
Heat transferred to the system
i P2 V2  P1V1
Work done on the system W  U  nRT 
2  1
C Pm i  2
The ratio of specific heats  
C Vm i
i 1

2  1
i2 
C Pm  R R
2  1
i 1
C Vm  R  R
2  1
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Heat capacity for ideal gases

i
The molar specific heat at constant volume : CV  R
2

i2
The molar specific heat at constant pressure Cp  R
2

The ratio of specific heats CP i  2

 
CV i

R R
CV  ; CP  ; CP  CV  R
 1  1
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ADIABATIC PROCESS
dU  Q  PdV
Adiabatic process : Q  0
dU   PdV
i
dU  nRdT
2
PV  nRT
PdV  VdP  nRdT
i i
dU  nRdT  ( PdV  VdP)
2 2
i
(PdV  VdP)   PdV
2
i2 i
PdV  VdP  0
2 2
i  2 dV dP
 0 PV   const  TV  1  const
i V P PV    1 
 ln V  ln P  ln C  const  T P  const
PV   Const T 
SUMMARY 18
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Exercise 1. We have oxygen gas with an amount of 40 g, volume of 3 l and pressure

10 at.
1. What is temperature of the gas?
2. This gas expands at constant pressure up to volume of 4l. What is the final
temperature?
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Exercise 1.

1) We have: PV=nRT
T=
2) Constant pressure process: V1/T1=V2/T2
T2=
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Exercise 2. We have hydrogen gas of 10 gr, at the pressure 8.2 at. in a can of 20l.
1. What is temperature of the gas?
2. The can of gas is heated up at constant volume to the pressure of 09 at. What is the
final temperature of the gas?
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Exercise 2.

1) We have: p1V=nRT1
T1=
2) For constant volume process: p1/T1=p2/T2
T2=
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Exercise 3. We have a gas of 10 gr stored in a can at pressure of 10^7 Pa. Gas is taken
partially from a can to pressure of 2.10^6 Pa. Process occurs at constant temperature.
What is amount of gas taken from the can?
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Exercise 3.

We have: p1V=n1RT
p2V=n2RT
Therefore,
p2/p1=n2/n1=m2/m1
Amount of gas taken from a can: m=(m1-m2)

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