Physics for Technical Students I

Chapter 18 & 19:

Heat and work
Idea gases
 The First Law of Thermodynamics
Eint = sum total of the energy of particles (molecules/atoms) in system
Internal Energy or Thermal Energy

Eint (increases) if work done to system or heat added to system

Eint (decreases) if work done by system or heat taken from system

Although W and Q are path-dependent, Eint is not.

E int E int,f E int,i Q Wby

dEint dQ dWby

In thermodynamics, Work is defined as done by system: Eint Q Won

 Vf

Path Dependence of Work and Eint Wby dW pdV

Vi

isobaric: W = pV E int E int,f E int,i Q W

W = 0
isochoric: dEint dQ dWby
Volume increases,
Pressure decreases: Two step: Figure shows four paths on p-V
area > 0 -> W > 0 Volume increases then diagram along which a gas can be
Pressure decreases:
(gas expands)
area > 0 -> W > 0 taken from state i to state f. Rank:
1) Eint ?
2) Work done by gas?
Work and Heat are NOT CONSERVATIVE: depends on path
3) Heat transferred?
Eint does NOT depend on path !!

NET WORK, Wnet, done by

system during a complete cycle is
shaded area. It can be pos., neg,
or zero depending on path. Around a closed cycle
Eint is zero.
 Special cases of First Law of Thermodynamics
E int E int,f E int,i Q W
1) Adiabatic processes - NO TRANSFER OF ENERGY AS HEAT Q = 0
a) rapid expansion of gasses in piston - no time for heat to be transferred
b) if work is done by system (W>0), then Eint decreases

c) NOTE: temperature changes!!
E int W adiabatic
V f Vi
2) Constant-volume processes (isochoric)- NO WORK IS DONE W=0
a) if heat is absorbed, the internal energy increases Wby pdV 0
Vi
b) NOTE: temperature changes!!
E int Q
3) Cyclical process (closed cycle) Eint,closed cycle =0
a) net area in p-V curve is Q
Eint 0 Q W

4) Free Expansion : adiabatic process with no transfer of heat
a) happens suddenly
b) no work done against vacuum E int Q W 0
c) non-thermal equilibrium process

5) Isothermal: Temperature does not change Well talk about this later

 Sample Problem 18-5
Let 1.0 kg of liquid at 100C be converted to steam at 100C by boiling
at twice atmospheric pressure (2 atm) as shown. The volume of the
water changes from an initial value of 1.010-3 m3 as a liquid to 1.671 m3
as a gas.

Here, energy is transferred from the thermal reservoir as heat until the
liquid water is changed completely to steam. Work is done by the expanding
gas as it lifts the loaded piston against a constant atmospheric pressure.
Vf

a) How much work is done by Wby pdV pV f Vi

Vi
the system during the process?
How do we calculate work? 2 atm1.01 10 5 N/m 2 atm1.671 m 3 0.001 m 3
338 kJ

b) How much energy is transferred

as heat during the process? no temperature change only phase change
Q mLV 1.0 kg2256 kJ/kg 2260 kJ
What is the heat added?

c) What is the change in the systems

internal energy during the process?
E int Q Wby
Using 1st Law of Thermo: 2260 kJ 338 kJ 1920 kJ

Positive! Energy mostly (85 %) goes into

separating H2O molecules

 More Example
18-43: Gas within a closed chamber undergoes the cycle shown in
the p-V diagram. Calculate the net energy added to the system as
heat (Q) during on complete cycle.

In one complete cycle, Eint,cycle = 0 so Q=W. To find Q, calculate W!

Wby WA B WB C WC A
VB VC VA

p
VA
A B dV p
VB
B C dV p
VC
CA dV 20 10
pA B (V ) V m -3 Pa
3 3
pB C (V ) 30 Pa
4 1 1

VC A 0
20
3
V 103 dV 30 dV pC A dV
1 4 1

1 m3
4 m3 1 m 3
20 1
V 2 103 V 30 V 0 30 J
3 2
4 m3

Or just add up area enclosed!

W = Q = - 30 J CCW - negative
CW - positive
 Chap. 19: Kinetic Theory of Gases
Thermodynamics = macroscopic picture
Gases = micro -> macro picture

IDEAL GAS LAW

n = number of moles N = number of particles

k = 1.3810-23 J/K
pV = nRT R = 8.315 J/(molK)
= 0.0821 (Latm)/(molK)
pV = NkT R = kNA = 1.99 calories/(molK)

Monoatomic ideal gas : He, Ar, Ne, Kr (no potential energies)

E int,monotonic N 32 kT 32 nRT
The internal energy
of an ideal gas depends
E int,monotonic 32 nRT only on the temperature
 Avogadros Number
One mole is the number of atoms in 12 g sample of carbon-12

C(12)6 protons, 6 neutrons and 6 electrons

12 atomic units of mass assuming mP=mn

NA=6.02 x 1023 mol-1

Another way to do this is

So the number of moles n is given by to know the mass of one
n=N/NA molecule: then
N=M(sample)/mNA
Ideal Gases, Ideal Gas Law pV nRT pV NkT
It was found experimentally that if 1 mole of any gas is placed in containers that
have the same volume V and are kept at the same temperature T , approximately all
have the same pressure p. The small differences in pressure disappear if lower gas
densities are used.

Further experiments showed that all low-density gases obey the equation pV nRT .
Here R 8.31 K/mol K and is known as the "gas constant." The equation itself is
known as the "ideal gas law." The constant R can be expressed as R kN A .
Here k is called the Boltzmann constant and is equal to 1.38 10-23 J/K.

N
If we substitute R as well as n in the ideal gas law we get the equivalent form:
NA
pV NkT . Here N is the number of molecules in the gas.

The behavior of all real gases approaches that of an ideal gas at low enough densities.
Low densities means that the gas molecules are far enough apart that they do not
interact with one another, but only with the walls of the gas container.
19-1: Gold has a molar mass of 197 g/mol. (a) How many moles of
gold are in 2.50g sample of pure gold? (b) How many atoms are in the
sample? Au has 79 protons and ~118 neutrons.

n is number of moles (19-3)

M sample M sample
n=
M (molar mass) m(one atom) N A

M sample 2.5g
n= 0.0127 mol.
M (molar mass) 197g / mol.

(b) Number of atoms Eqn. 19.2

N
n= or N=n N A
NA
N 0.0127 6.02 1023 7.64 1021
19.2: Find the mass in kilograms of 7.5 x 1024 atoms of arsenic, which
has a molar mass of 74.9 g/mole. As has 33 protons and ~42 neutrons

M
Each atom has a mass m
NA
Where M is the molar mass

The molar mass of As is 74.9 g/mol.

Total M
7.5 10 74.9 10 kg / mol
24 3

6.02 10 mol
24 1

M 0.933 kg
19-3: The best laboratory vacuum has a pressure of about 1.00 x
10-13 Pa or 10-18 atm. How many gas molecules are there per
cubic centimeter in such a vacuum at 293 K?

Get units straight Ideal gas Law

V 1.0 106 m3 pV nRT
p 1013 Pa R gas constant
T 293 K R 8.31 J / mol. K

n
pV

10 13
Pa 106 m3
4.1x1023 mole
RT 8.31J / mol.K 293K

N nN A 4.1x1023 mole 6.02 x1023 mole 1 25 molecules

Work done by isothermal (T = 0) expension of ideal gas
On p-V graph, the green lines are isotherms
each green line corresponds to a system at a constant temperature.

From ideal gas law, this means that for a given isotherm:
1
pV constant p nRT Relates p and V
V
V f
The work done by the gas is then: Wby,isothermal nRT ln

T =0 Vi
Vf Vf Vf
nRT dV p
Wby pdV
Vi
V


dV nRT V nRT ln i
p f
Vi Vi

Work done by isobaric (P = 0) expansion of an ideal gas

Wby,isobaric pV
P=0

nRT
Work Done by an Ideal Gas at Constant Temperature
Consider the gas shown in the figure. It is held at a
constant temperature T and undergoes an isothermal
expansion from volume Vi to volume V f . The process
follows the red line on the lower figure. The work
W done by the ideal gas is given by the equation
Vf

W p dV . From the ideal gas law we have that

Vi
Vf Vf
nRT nRT dV
dV nRT
Vf
p W nRT lnV V ;
V Vi
V V
V i
i

Vf
W nRT ln .
Vi
Vf
For expansion we have : V f Vi ln 0 W 0.
Vi
Vf
For compression we have : V f Vi ln 0 W 0.
Vi
Sample problem 19-2: One mole of oxygen expands at a constant
temperature T of 310 K from an initial volume Vi of 12 L to a final volume
Vf of 19 L. How much work is done by the gas during the expansion.

We calculated W for isothermal expansion

W = nRT ln (Vf /VI)

W = (1 mole)(8.31J/mole K)(310K) ln(19/12)

W = 1180 J
 Summary
pressure i
Work Done by an Ideal Gas at Constant Volume
Consider process i f . and V contant.
f
The work W done by the gas is W pdV 0.
volume
Work Done by an Ideal Gas at Constant Pressure
pressure

Consider process i f . and P contant.

i f The work W done by the gas is
Vf Vf

volume W pdV p dV p V
Vi Vi
f Vi .

Work Done by an Ideal Gas at Constant Temperature

i Consider process i f . and T contant.
pressure

Vf

W pdV . From the ideal gas law we have that

f Vi
V V
nRT
f
nRT
f
dV V
volume p W dV nRT nRT ln f
V Vi
V Vi
V Vi