Lecture 2 The First Law of

Thermodynamics (Ch.1)

Outline:
1. Internal Energy, Work, Heating
2. Energy Conservation the First Law
3. Quasi-static processes
4. Enthalpy
5. Heat Capacity
 Internal Energy
The internal energy of a system of particles, U, is the sum of the kinetic
energy in the reference frame in which the center of mass is at rest and the
potential energy arising from the forces of the particles on each other.

system Difference between the total energy and the internal energy?
boundary system
U = kinetic + potential
environment
B The internal energy is a state function it depends only on
P
the values of macroparameters (the state of a system), not
on the method of preparation of this state (the path in the
T V macroparameter space is irrelevant).
A

In equilibrium [ f (P,V,T)=0 ] : U = U (V, T)

U depends on the kinetic energy of particles in a system and an average
inter-particle distance (~ V-1/3) interactions.

For an ideal gas (no interactions) : U = U (T) - pure kinetic

 Internal Energy of an Ideal Gas

f
The internal energy of an ideal gas
with f degrees of freedom:
U = Nk BT
2
f 3 (monatomic), 5 (diatomic), 6 (polyatomic)

(here we consider only trans.+rotat. degrees of freedom, and neglect

the vibrational ones that can be excited at very high temperatures)

How does the internal energy of air in this (not-air-tight) room change
with T if the external P = const?

f PV f
U = N in room k BT = N in room = = PV
2 k BT 2

- does not change at all, an increase of the kinetic energy of individual

molecules with T is compensated by a decrease of their number.
 Work and Heating (Heat)
WORK

We are often interested in U , not U. U is due to:

Q - energy flow between a system and its
environment due to T across a boundary and a finite HEATING
thermal conductivity of the boundary
heating (Q > 0) /cooling (Q < 0)
(there is no such physical quantity as heat; to
emphasize this fact, it is better to use the term
heating rather than heat)
W - any other kind of energy transfer across
boundary - work

Work and Heating are both defined to describe energy transfer

across a system boundary.
Heating/cooling processes:
conduction: the energy transfer by molecular contact fast-moving
molecules transfer energy to slow-moving molecules by collisions;
convection: by macroscopic motion of gas or liquid
radiation: by emission/absorption of electromagnetic radiation.
 The First Law
The first law of thermodynamics: the internal energy of a system can be
changed by doing work on it or by heating/cooling it.

U = Q + W conservation of energy.

Sign convention: we consider Q and W to be positive if energy

flows into the system.
P
For a cyclic process (Ui = Uf) Q = - W.
If, in addition, Q = 0 then W = 0
T V

An equivalent formulation:
Perpetual motion machines of the first type do not exist.
 Quasi-Static Processes
Quasi-static (quasi-equilibrium) processes sufficiently
slow processes, any intermediate state can be considered
as an equilibrium state (the macroparamers are well-
defined for all intermediate states).

Advantage: the state of a system that participates in a quasi-equilibrium

process can be described with the same (small) number of macro
parameters as for a system in equilibrium (e.g., for an ideal gas in quasi-
equilibrium processes, this could be T and P). By contrast, for non-
equilibrium processes (e.g. turbulent flow of gas), we need a huge number
of macro parameters.

Examples of quasi- For quasi-equilibrium processes, P, V, T are

equilibrium processes: well-defined the path between two states
is a continuous lines in the P, V, T space.
isochoric: V = const P 2
isobaric: P = const
isothermal: T = const
1 V
adiabatic: Q=0 T
 Work
The work done by an external force on a gas
A the enclosed within a cylinder fitted with a piston:
piston
area W = (PA) dx = P (Adx) = - PdV
force

The sign: if the volume is decreased, W is positive (by

x
compressing gas, we increase its internal energy); if the
volume is increased, W is negative (the gas decreases
its internal energy by doing some work on the
P environment).

V2
W1 2 = P(T , V )dV
V1
W = - PdV - applies to any
shape of system boundary dU = Q PdV
The work is not necessarily associated with the volume changes e.g.,
in the Joules experiments on determining the mechanical equivalent of
heat, the system (water) was heated by stirring.
 W and Q are not State Functions
V2 - we can bring the system from state 1 to
W1 2 = P (T , V )dV state 2 along infinite # of paths, and for each
V1
path P(T,V) will be different.
P 2
Since the work done on a system depends not
only on the initial and final states, but also on the
1 V intermediate states, it is not a state function.
T

U = Q + W U is a state function, W - is not

thus, Q is not a state function either.
P

P2
A B Wnet = WAB + WCD = P2 (V2 V1 ) P1 (V1 V2 )
= (P2 P1 )(V2 V1 ) < 0
P1 D C
- the work is negative for the clockwise cycle; if
the cyclic process were carried out in the reverse
V1 V2 V order (counterclockwise), the net work done on
the gas would be positive.
PV diagram
 Comment on State Functions
U, P, T, and V are the state functions, Q and W are not. Specifying an initial and final
states of a system does not fix the values of Q and W, we need to know the whole
process (the intermediate states). Analogy: in classical mechanics, if a force is not
conservative (e.g., friction), the initial and final positions do not determine the work, the
entire path must be specified.
In math terms, Q and W are not exact differentials of some functions
of macroparameters. To emphasize that W and Q are NOT the state U
functions, we will use sometimes the curled symbols (instead of d)
for their increments (Q and W).
V
d U = T d S P dV - an exact differential S

y z(x1,y1) dz = Ax ( x, y ) dx + Ay ( x, y ) dy - it is an exact differential if it is

the difference between the values of some (state) function
z(x2,y2)
z(x,y) at these points: dz = z ( x + dx, y + dy ) z ( x, y )
x Ax ( x, y ) Ay ( x, y )
A necessary and sufficient condition for this: =
y x
z ( x, y ) z ( x, y ) z z
Ax ( x, y ) = Ay ( x, y ) =
If this condition
d z = dx + dy
holds: x y x y y x
f T
e.g., for an ideal gas: Q = dU + PdV = Nk B dT + dV - cross derivatives
2 V are not equal
 Problem

Imagine that an ideal monatomic gas is taken from its initial state A to state
B by an isothermal process, from B to C by an isobaric process, and from
C back to its initial state A by an isochoric process. Fill in the signs of Q,
W, and U for each step.
P,
105 Pa Step Q W U
A
2
AB + -- 0
T=const
BC -- + --
B
1 C
CA + 0 +
1 2 V, m3

f PV = Nk B T
U = Nk BT
2
 Quasistatic Processes in an Ideal Gas

isochoric ( V = const )
P
2 W12 = 0

Q12 = NkB (T2 T1 ) > 0 (= CV T )

PV= NkBT2
3
1 PV= NkBT1 2
(see the last slide)
V1,2 V dU = Q12
isobaric ( P = const )
P 2
W12 = P(V , T )dV = P(V2 V1 ) < 0
2 1
1 PV= NkBT2
Q12 = NkB (T2 T1 ) > 0 (= CPT )
5
PV= NkBT1
2
V1 V2 V
dU = W12 + Q12
 Isothermal Process in an Ideal Gas

P isothermal ( T = const ) :

PV= NkBT
dU = 0
W V2 V2
dV V
V2 V1 W12 = P (V , T )dV = Nk BT = Nk BT ln 2
V V V1
V1 V1

V Q12 = W12
Wi f = Nk BT ln i
Vf
Wi-f > 0 if Vi >Vf (compression)
Wi-f < 0 if Vi <Vf (expansion)
 Adiabatic Process in an Ideal Gas
adiabatic (thermally isolated system) Q12 = 0 dU =W12
The amount of work needed to change the state of a thermally isolated system
depends only on the initial and final states and not on the intermediate states.
V2

W12 = P(V , T )dV

P V1
2
to calculate W1-2 , we need to know P (V,T)
for an adiabatic process
PV= NkBT2
1 f f
PV= NkBT1 U= Nk BT dU = Nk B dT = PdV
2 2
V2 V1 V ( f the # of unfrozen degrees of freedom )

2
PV = Nk BT PdV + VdP = Nk B dT PdV + VdP = PdV PV
f
V P
dV 2 dP 2 Adiabatic dV dP
1 + + =0 , = 1+ + =0
V f P f exponent V1
V P1
P

V P
ln = ln 1 PV = P1V1 = const
V1 P
 Adiabatic Process in an Ideal Gas (cont.)

P PV = P1V1 = const
2
An adiabata is steeper than an isotherma:
PV= NkBT2 in an adiabatic process, the work flowing
1 out of the gas comes at the expense of its
PV= NkBT1
thermal energy its temperature will
V2 V1 V decrease.
V2 V2 V2
PV 1
W1 2 = P(V , T )dV = 1 1
dV = PV
V +1

V + 1
1 1
V1 V1 V1

1 1 1
= PV 1 1
1 V2
1 1
V1
1+2/31.67 (monatomic), 1+2/5 =1.4 (diatomic), 1+2/6 1.33 (polyatomic)
(again, neglecting the vibrational degrees of freedom)
f f
Prove W1 2 = ( PV ) = Nk B T = U
2 2
 Summary of quasi-static processes of ideal gas
U U f U i

Quasi-Static Ideal gas

U Q W
process law
isobaric f f f +2 Vi V f
U = Nk B T = P V PV PV =
(P=0) 2 2 2 Ti T f
isochoric U = f Nk T = f P V f Pi Pf
B ( ) ( P )V 0 =
Ti T f
(V=0) 2 2 2
isothermal Vf
0 W Nk B T ln i i = Pf V f
PV
(T=0) Vi

adiabatic U = f Nk T = f PV
( ) 0 U i i = Pf V f
PV
B
(Q=0) 2 2
 Problem
Imagine that we rapidly compress a sample of air whose initial pressure is
105 Pa and temperature is 220C (= 295 K) to a volume that is a quarter of
its original volume (e.g., pumping bikes tire). What is its final temperature?
Rapid compression approx. adiabatic, no time for the energy
exchange with the environment due to thermal conductivity

P1V1 = Nk BT1 1

P1V1
P1V1 P1V1 V1 T2
P2V2 = Nk BT2 P2 = = Nk T = T2 =
V2 V2 1
B 2
T1 V2 T1
P1V1 = P2V2
1 1
For adiabatic processes: T1 V1 = T2 V2 = const
also P 1 / T = const
1
V1
T2 = T1 = 295 K 4 0.4 295 K 1.74 514 K
V2
- poor approx. for a bike pump, works better for diesel engines
 Non-equilibrium Adiabatic Processes
Free expansion
1. TV 1 = const V increases
T decreases (cooling)

2. On the other hand, U = Q + W = 0

U ~ T T unchanged
(agrees with experimental finding)

Contradiction because approach

#1 cannot be justified violent
expansion of gas is not a quasi-
static process. T must remain the
same.

TV 1 = const - applies only to quasi-equilibrium processes !!!

 The Enthalpy
Isobaric processes (P = const):

dU = Q - PV = Q -(PV) Q = U + (PV)

H U + PV - the enthalpy
The enthalpy is a state function, because U, P,
and V are state functions. In isobaric processes,
the energy received by a system by heating equals
to the change in enthalpy.
in both cases, Q
isochoric: Q=U does not
depend on the
isobaric: Q=H path from 1 to 2.

Consequence: the energy released (absorbed) in chemical reactions at constant

volume (pressure) depends only on the initial and final states of a system.
f f
The enthalpy of an ideal gas: H = U + PV = Nk BT + Nk BT = + 1 Nk BT
(depends on T only) 2 2
 Heat Capacity

The heat capacity of a system - the amount of energy

Q
transfer due to heating required to produce a unit C
temperature rise in that system T
T
f1 f2 f3
C is NOT a state function (since Q is not a T1+dT
state function) it depends on the path
between two states of a system T1
i
V
( isothermic C = , adiabatic C = 0 )

C
The specific heat capacity c
m
 CV and CP

U the heat capacity at

CV =
Q dU + PdV T V constant volume
C= =
dT dT
H the heat capacity at
CP =
T P constant pressure

To find CP and CV, we need f (P,V,T) = 0 and U = U (V,T)

f f
U = Nk BT
For an ideal gas H = + 1 Nk BT
2 2
f f f
CV = Nk B = nR CP = + 1 nR
2 2 2
# of moles
3 5
For one mole of a CV = R CP = R
monatomic ideal gas: 2 2
 Another Problem P
Pi
During the ascent of a meteorological helium-gas filled balloon,
its volume increases from Vi = 1 m3 to Vf = 1.8 m3, and the
pressure inside the balloon decreases from 1 bar (=105 N/m2) to Pf
0.5 bar. Assume that the pressure changes linearly with volume
between Vi and Vf.
(a) If the initial T is 300K, what is the final T?
(b) How much work is done by the gas in the balloon? Vi Vf V
(c) How much heat does the gas absorb, if any?
P(V ) = 0.625 bar/m 3 V + 1.625 bar

(a) PV Pf V f 0.5bar 1.8m 3

PV = Nk B T T= T f = Ti = 300K = 270K
Nk B Pi Vi 1bar 1m 3

Vf Vf
(b) WON = P (V )dV - work done on a system WBY = P (V )dV - work done by a system
Vi
Vi
Vf

WON = WBY WBY = P(V )dV = (0.5 0.8 bar m3 + 0.5 0.4 bar m3 ) = 0.6bar m3 = 6 10 4 J
Vi

(c) U = Q + WON
T
Q = U WON = NkB (T f Ti ) WON = Pi Vi f 1 + WBY = 1.5 105 J ( 0.1) + 6 104 J = 4.5 104 J
3 3
2 2 Ti