Thermodynamics

B Kuswandi
adapted from open sources
 Thermodynamics
• The 19th century industrial revolution was powered by the
practical applications of the new understanding of the
theoretical connection between heat and mechanics.
• Thermodynamics is the study of the connection between
mechanics and average internal properties of a large system.
• In spite of its ‘approximate’ character, Thermodynamics has
emerged essentially intact, even strengthened by the twin
20th century revolutions of Relativity & Quantum Mechanics
• Thermodynamics has also made important contributions to
Cosmology.
 Heat and Energy

• Dissipative mechanical processes produce heat.

 E < 0
• As a gas is heated, the pressure increases,
 If the gas is allowed to expand in a piston, the gas does
mechanical work on its surroundings
 E > 0
 “Zeroth” law of Thermodynamics
(but last to be enumerated)
• If object A is in thermal equilibrium with
object C,
A C
• And object B is in thermal equilibrium with
object C,
• Then object A & B are also in thermal
equilibrium. B
• Thermal Equilibrium = Same temperature
• Thermal Equilibrium = No heat flow
• BUT: we often speak of a system in
equilibrium heat flow between a system and a
heat bath, which will happen if the two are at
infinitessimally different temperatures.
T

TT
 A Zen Koan for Zeroth Law of
Thermodynamics
(If it is so obvious, how come no one thought of it until after
Laws 1, 2, & 3)

• If system A and system B are in thermal equilibrium with each

other, then by definition no heat flows from A to B (or vice-
versa).
• In many thought-experiments (and real experiments) of
thermodynamics, a system A is in thermal equilibrium with a
much larger system B.
 B is called a “heat bath”
• The purpose of B is for B to keep a constant temperature, while
exchanging any amount of heat (+ or -) from A.
• But how can A & B exchange heat if they are in thermal
equilibrium (which was the whole point, B regulates the
temperature of A)???
 First Law of Thermodynamics
Conservation of Energy
• In addition to mechanical energy (Kinetic Energy K, potential
energy V) a system has internal [thermal] energy we label U.
• In any interaction of the system with its surroundings in
which the system does mechanical work W and heat Q flows
into the system, energy conservation requires that the change
in internal energy of the system equals the heat flow in minus
the work done (note signs).
• U = Uf Ui = Q  W
• Ultimately, Internal energy is not a “new” form of energy—it
is just the kinetic and [chemical=electromagnetic] potential
energy of the atoms and molecules that make up the matter of
our system.
 U, W, Q
• W = work done by a system on its surroundings
• Q = Heat flow into system (Q<0 for heat flowing out).
• W and Q depend upon the particular process (e.g., path in a
Pressure vs Volume plot).
• U = internal (thermal) energy of system.
• U depends only on the present state of the system (not on how
it got there).
• For an ideal gas, U is a function only of Temperature.
 Monoatomic ideal gas (He, Ne, Ar…) U = (3/2) RT
 Diatomic ideal gas (O2, N2,…) U = (5/2) RT
• Need Quantum Mechanics to prove this!
 Internal Energy of an ideal gas.
• Ideal gas: U is a function only of temperature, not of P, V
separately.
 U(ideal gas) = kinetic energy of molecules + internal rotational and
vibrational energy. This is independent of the volume.
 Place an ideal gas in a container of volume V. Suddenly double the
volume (open a valve to a 2nd container), kinetic energy of gas does
not change, the gas does no work.
 Temperature does not change, U is unchanged.

Kinetic Theory simulations:

http://physics.weber.edu/schroeder/software/
 First Law of Thermodynamics
Special case I. Constant Volume
• The system does no work (a
gas at fixed volume)
 Change in internal energy = Heat
flow in
 U = Q = n CV T

CV = molar specific heat at

constant volume
 First Law of Thermodynamics
II. Thermally isolated
• No heat flows in or out of the system
 A gas expands in a piston, but the system is
thermally isolated, the expansion happens too
fast for any significant exchange of heat.
 U = W
 Thermal energy is converted to work.
 If Uf Ui then the system does positive work on
its surroundings.
 Thermal Processes
Expansion at Constant Pressure
• A gas expands, pushing a piston at constant
pressure.
 The gas exerts a force F = P A against the piston
 The gas does work W = F(xf-xi)
 W = P A (xf-xi)
 W = P (A xf- A xi )
 W = P (Vf – Vi)
 W = P V

Work = Area under a

pressure vs. Volume curve
 Constant Pressure Expansion:
Example
• Approximate the power stroke of a 4-cylinder automobile
engine by a constant pressure expansion at P = 10 atm with
a change in volume of V=0.5 litre. If the engine is
running at 3000 rpm, what is the total power output of the
engine in Watts, and Horsepower.
• Find the engine torque.

1 litre = (10 cm)3 = (0.1 m)3 = 1.0·103 m3

T = time for one complete engine cycle
Four stroke engine, T = two engine revolutions
T = 2/f = 2 / [3000 revolutions / min]
T = (1 min) / 1500 = (60 sec/min)(1 min/1500) = 1sec/25 = 0.04 s
 Engine Power, cont’d
Work done by one cylinder:
W = PV = 10(105 N/m2) (0.5 ·103 m3)= 5 ·10 N · m
Total power = rate at which all four cylinders do work
Power = 4 W / T
Power = 4 (5 ·10 J) / (0.04 sec) = 50 kWatt
Power = (50 kWatt) [(1 hp)/(746 W)] =67 hp
Power = force times velocity = Torque times angular velocity
(chap 10, not on exams)
Torque = power divided by angular velocity
Angular velocity = 2 f = (2) 3000/min = 2 50/sec = 314/sec
Torque= (50kW) / (314/s) = 16 N · m
Convert N · m to ft·lb.
2.2lb = (1kg)(g) = 9.8 N
1ft  30 cm
Torque = [16 N · m ] [2.2lb/9.8N] [1ft/0.3m] =12 ft·lb.
 Ideal Gas Molar Heat Capacity at
Constant Pressure
• An ideal gas expands against a constant pressure from C to B:
• U = QCB – WCB
• UBUC = nCP(TBTC) – PC (VBVC) = nCP(TBTC) – n R(TBTC)
• CP = molar heat capacity at constant pressure
• If instead the gas is heated
from C to A,
• UAUC = nCV(TATC)
• Also, UB = UA (isotherm)
• UAUC = UBUC
• CP = C V + R
 Thermal Processes
Idealized Reversible Processes
• An [ideal] gas is confined by a piston, which exerts a
variable pressure P. The gas is isolated, no heat enters or
leaves the gas.
• The external pressure P slowly compresses the gas
 Ideal Gas Law, PV = n R T
 As the piston compresses the gas, the gas does work on the piston:
W = PV < 0
 The internal energy of the gas rises U = Q -W =-W >0
 If the internal energy rises, the temperature rises.
 We will find out how to calculate the temperature rise later.
 Reversible Process with Heat Bath
(Isotherm)
• An [ideal] gas is confined by a piston, which exerts a variable
pressure P.
• The gas is in contact with a heat bath at temperature T.
 The external pressure P slowly compresses the gas, this tends to head
the system to temperature T+T, but heat flows out of the system to
the heat bath, keeping its constant temperature T.
 Now reverse the process, the gas expands against the pressure P, Heat
flows into the system to keep the temperature constant
 0 = U = Uf Ui = Q W
Isotherms
PV=nRT
P=nRT/V
 Work done by system in isothermal
process (T= constant)
• 0 = U = Q-W Q=W
• Volume changes from Vi to Vf
 Break up process into small steps
 Volume changes by V << V with each step.

Work done by system

W  P1V  P2V  ...
 V V 
 (nRT )    ...
 V1 V2 
V f 
 (nRT ) ln  
 Vi 
 Logarithms
• Log(u) = v means: 10v = u
• ln(x) = y means: ey=x e=2.71828…
if ey=x, ln(x) = ln[ey] = y by definition of ln().
Logarithms are just a way of making big numbers small
log(10 trillion) = 13;
and turning multiplication into addition:

if e y1  x1, and e y2  x 2 , then

e0  1
y1  ln x1, and y2  ln x2
y1  y2
0  ln 1
e y1 e y2 e
ln( x1x2 )  ln x1  ln x2
e y  1 for y  0
ln( x1 / x2 )  ln x1  ln x2 lnx  0 for 0  x  1
 Otto Cycle

• 4-stroke:
 1) Compress fuel/air mixture
 Explosive burn (nearly
instantaneous).
 2) Adiabatic expansion
 3) Exhaust
 4) Fuel/Air intake
 Adiabatic Process
(thermally isolated system, no heat in or out)
• Need Calculus to
show:
 PV = constant
  = Cp / C V
 Calculus also needed
to calculate work
done.
• U = QW
• U = W
 2nd Law of Thermodynamics

• First Version:
 When objects of different temperature are brought into
thermal contact, the spontaneous flow of heat is always
from the hotter object to the cooler object
 Heat Engine
• A heat engine is a mechanical system that
as it cycles through a repetitive motion,
transfers heat from a high temperature
heat bath to a low temperature bath, and
performs work on its environment
 Qh = W + Q c
• Examples:
 Diesel cycle:
auto.howstuffworks.com/diesel.htm
 Otto cycle (gasoline engine)
 Stirling Engine
 Carnot cycle (idealized heat engine).
 Carnot Cycle
• Isothermal expansion
 Heat in from high
temperature bath
 W1 > 0
• Adiabatic expansion
 No heat in or out
 W2 > 0
• Isothermal Compression
 Heat dumped into low
temperature bath
 W3 < 0
• Adiabatic Compression
 No heat in or out The heat engine alternates between
 W4 < 0 contact with high and low
temperature reservoirs
• Net work = shaded area =
net area under P vs V graph.
 Carnot Cycle Efficiency
• In the ideal Carnot cycle, a heat engine operates in a closed
loop, absorbing heat QH at high temperature TH, and
discharging heat QC at cool temperature TC, while doing work
W. The efficiency is defined by
 Efficiency e = W/QH a
 For the ideal carnot cycle, e = 1 – T C/TH
• (temperature measured from absolute zero).
• 2nd Law of Thermodynamics (heat engine version):
 A heat engine has maximum efficiency if all proceses are reversible
 All heat engines operating between T C & TH have the same efficiency
 No heat engine, operating between temperatures T H and TC can have a
higher efficiency than the Carnot cycle.
 Walker, problem 86

• A mole of an ideal monoatomic gas follows the

three part cycle shown. Fill in the table, and find
the efficiency of this cycle.
Q W U

AB

BC

CA
 Walker, problem 86, solution
• BC, constant pressure compression
 W = P V, note V=(VC-VB) < 0
 Q = n CP T
 Use PV = nRT to find TB, TC
 U = Q-W = nCP T - P V = nCP T – n R T = nCV T
 Ideal Gas: U= nCV T: U = nCV T

• CA, Constant volume heating

• W = 0 (no change in volume)
• Q = nCV T
• U = Q – W = nCV T
• AB, Isotherm, U = 0
•W = n R ln[VB/VA]
• 0 = U = Q – W
•Q=W
 Steam Engine: Not an ideal gas!!
• In the piston, the hot water vapor
expands along an adiabad: no heat
in or out.
• In the condensor, the water vapor
(T=100C) condenses to liquid
(T=100C) while liberating heat
Latent heat to the heat bath
(T<100C)
• The pump maintains the pressure
difference between condensor and
boiler. Since liquid is almost
incompressible, pump does almost
no work.

boiling
• In the boiler, the water at 100C Adiabad
absorbs latent heat from heat bath
(T>100C) and boils.
condensing
 Heat Pump
• A heat engine, run in reverse, is a heat pump.
 It pumps heat from the cool temperature to the hot temperature.
 This violates the 2nd law of thermodynamics—NOT, because the
net work done by the system is negative (There must be work done
on the system).
• Examples
 Refridgerator
• What happens to temperature in room if you leave the refridgerator
door open?
 Air Conditioner
 Heat pump for heating house.
• Coefficient of performance QH/W
 Entropy = Measure of Disorder

• Entropy is a state variable (like thermal energy)

• Changes in entropy S:
 S = Q/T

• Chocolate chip motor = Entropy engine (see my

web page).
 Third Law of Thermodynamics

• It is impossible to reach absolute zero in a finite

number of steps.