Lecture 2 The First Law of Thermodynamics

(Ch.1)

Lecture 1 - we introduced macroscopic parameters that describe

the state of a thermodynamic system (including temperature), the
equation of state f (P,V,T) = 0, and linked the internal energy of
the ideal gas to its temperature.

Outline:
1. Internal Energy, Work, Heating
2. Energy Conservation – the First Law
3. Enthalpy
4. 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

The internal energy of an ideal gas f

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
From the microscopic point of view, this statement is equivalent to
a statement of 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.

Perpetual motion machines come in two types: type 1 violates

the 1st Law (energy would be created from nothing), type 2 violates
the 2nd Law (the energy is extracted from a reservoir in a way that
causes the net entropy of the machine+reservoir to decrease).
 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 Joule’s 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) d a  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: d a  z x  dx, y  dy   z x, y 
x Ax x, y  Ay x, y 
A necessary and sufficient condition for this: 
y x
If this condition z x, y  z x, y   z   z 
Ax x, y   Ay x, y   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
AB + -- 0
T=const
BC -- + --
B
1 C
CA + 0 +
1 2 V, m3
 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 (=10 5 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

PV   0.625 bar/m3  V  1.625 bar

(c) How much “heat” does the gas absorb, if any?

(a) PV  Nk T PV Pf V f 0.5bar  1.8m 3

B 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  Nk B 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 
 Quasistatic Processes in an Ideal Gas

isochoric ( V = const )
P
2 W12  0
3
PV= NkBT2 Q12  Nk B T2  T1   0  CV T 
1 PV= NkBT1 2
(see the last slide)
V1,2 V dU  Q12

isobaric ( P = const )
P 2
W12    P(V , T )dV   PV2  V1   0
2 1
1 PV= NkBT2 5
PV= NkBT1 Q12  Nk B T2  T1   0  CP T 
2
V1 V2 V
dU  W12  Q12
 Isothermal Process in an Ideal Gas

P isothermal ( T = const ) :

PV= NkBT
dU  0
W V2 V2
dV V
V2 V1 W12    P (V , T )dV   Nk BT    Nk BT ln 2
V V V1
V1 V1

V Q12  W12
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) Q12  0 dU  W12
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

W12    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
dV  2  dP 2 V
dV
P
dP
V
1   
 f  P
0  ,   1
f
 
V P1 P
0
V1

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
P1V1
W12    P (V , T )dV     dV
V1 V1
V
1  1 1 
 P1V1
   1 

  1  V2  1
V1 
  1+2/31.67 (monatomic), 1+2/5 =1.4 (diatomic), 1+2/6 1.33 (polyatomic)
(again, neglecting the vibrational degrees of freedom)
 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 bike’s 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  40.4  295 K 1.74  514 K
 V2 
- poor approx. for a bike pump, works better for diesel engines
Non-equilibrium Adiabatic Processes
(Joule’s Free-Expansion Experiment)

TV  1  const - applies only to quasi-

equilibrium processes !!!

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.
 The Enthalpy
Isobaric processes (P = const):

dU = Q - PV = 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

nst  U  the heat capacity at

= c o CV   
Q dU  PdV
V  T V constant volume
C  P=
dT dT con
st
 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)

dU  PdV   U   U  
C  dU    dT    dV 
dT   T V  V T 
 U   U   dV
      P
 T V  V T  dT

 U   dV 
C P  CV     P  
 V T  dT  P
 CV and CP for an Ideal Gas

For an ideal gas CV = dU/dT

CV of one mole of H2
f 7/2NkB
U Nk BT Vibration
2
5/2NkB
f f Rotation
CV  Nk B  nR 3/2NkB
2 2
Translation

# of moles 10 100 1000 T, K

 U   dV  f 
C P  CV     P 
Nk
  P B  Nk B
C P  CV  Nk B    1 Nk B
 V T  dT  P P 2 
f 
0    1nR
 R ( for one mole ) 2 
3 5
For one mole of a monatomic ideal gas: CV  R CP  R
2 2