You are on page 1of 52

# Thermodynamics

## Heat and Temperature and Thermodynamic Equilibrium

Heat Capacity
Specific Heat
Heat Transfer
Thermal Energy Balance
BIG PICTURE: The big ideas are Temperature and Heat. Temperature is a property
common to systems in thermodynamic equilibrium. Temperature is quantified in SI
units using the kelvin scale, defined by gas thermometers. Heat is energy in transit
as a result of a temperature difference.

Temperature

## Temperature seeks to quantify a macroscopic property of a system which describes

how hot or how cold and object is, in relation to other objects. Objects in contact,
at the same temperature, are in thermodynamic equilibrium.

## Gas Thermometers and the Kelvin Scale

Kelvin (K) are the units of absolute temperature. There is no temperature less than
0, it is unphysical. 0 is the melting point of ice at standard pressure, whereas
100 is the boiling point of water. The interval = = .
The two scales are related by

: = + .

## A great documentary on the historical

quest to reach the limit of temperature

## A shit film on the ultimate showdown

between man and the elements

## Table 16.1 P268

Empirically if a given amount of energy is added to a system, transferred to it as
Heat (), then this causes a temperature rise (), inversely proportional the
amount of material () and a material specific constant called the specific heat ().

Either =
or more commonly =

## Heat Capacity and Specific Heat

How much heat does it take to bring a 3.5 iron frypan from
20 to 120. If a 2stovetop heats the pan, how long will
this take. ( = 447 1 1 )

## Heat Capacity (C) of an object is given by (mass multiplied by specific heat).

The same 3.5 iron frypan at 120 is plunged into a plastic sink
filled with 2 of water at 20 . What is the equilibrium
temperature. ( = 447 1 1, = 4184)
= =

= 0

1 1 1 + 2 2 2 = 0

1 1 + 2 2 = 1 1 1 + 2 22

1 1 1 + 2 22
=
1 1 + 2 2

=
3.5 447 + 2 4184

= 308.75 = 36

## Calorimetry is the process of quantifying thermal energy transfer between objects

that are brought together and left to reach thermal equilibrium. i.e. mixing of fluids
Energy is assumed to be conserved =

Heat Transfer

conduction

convection

radiation

Usually for a given situation one mechanism will dominate however in some
cases all three need to be considered simultaneously.

Conduction

## Conduction is heat transfer through direct physical contact. Materials are

quantified by their thermal conductivity ( 1 1).

Conduction

## Conduction is heat transfer through direct physical contact. Materials are

quantified by their thermal conductivity ( 1 1).

Q
T
H=
A
t
x
heat flows from
high T to low T

dT
H = kA
dx

temperature
gradient

## thermal conductivity (W/m C)

Heat flow is the rate of heat transfer by conduction. The larger the area the
greater the heat flow. The higher the thermal conductivity the greater the
heat flow. Heat flow is driven by a temperature gradient, so the larger the
temperature difference the greater the heat flow.

Thermal Resistance

## Consider the temperature differences that occur

across a composite slab of different k materials.

(T3 T2 )
(T2 T1 )
= k1 A
H = k2 A
x1
x2

## Express H in terms of T only by defining the

thermal resistance of a single slab R (K/W)

HR2 = T2 T3

HR1 = T1 T2
Heat flow

ADD, H SUBJECT

dT
H = kA
dx

T1 T3
H=
R1 + R2

Thermal Resistances
add in series
= 1 + 2

Thermal Resistance

x
R=
kA

PHYSCAST ALERT

= 1 + 2

## Understanding Links: Thermal Resistance is analogous to Electrical Resistance

( ). Temperature difference is analogous to the potential difference
( ) and Heat flow is analogous to electrical current (H ).

Convection

Convection

## Natural convection relies on

the buoyancy effect alone to
move the fluid.

## Forced convection drastically

increases the fluid movement
by using a fan or pump.

## Calculations for convection are extremely complicated due to fluid dynamics

and remains one of the important unsolved problems in science.

Radiation

## All objects (with T0 K) radiate electromagnetic waves which carry away

energy. For everyday temperatures this radiation is in the infrared region.

## Stefan-Boltzmann Law for Radiated Power

= 4

= : 0 1 (0 , 1 : /)
= 5.67 108 2 4 Stefan Boltzmann constant

## An electric current passes through a metal strip 0.5 by 5 by

0.1, heating it at a rate of 50W. The strip has an emissivity = 1
and its surroundings are 300. What will be the strips temperature if
its enclosed in a vacuum bottle transparent to all radiation ?

Interpret

Evaluate

## Problem about energy transfer

Radiation dominant mechanism

= =

= ( 4 4 )

Develop

## Strip is flat 2D, Area = 52

=

=?

= 300

In equilibrium so =

+ 4

50
+ 3004
4
8
1 5 10 5.67 10

= 1153 = 880

Assess

## A poorly insulated water heater loses heat by conduction at the rate of

120 for each degree Celsius difference between the water and its
surroundings. Its electrically heated at 2.5 in a basement of 15.
What is the water temperature if the heating element operates
continuously ?

Thermal Energy Balance is where the heat gains are equal to the
heat losses and the system stays in equilibrium.

Summary

## Heat is energy in transit and results due to temperature differences

Specific Heat is a material property
Calorimetry is conservation of thermal energy !

## Temperature drops across thermally resistive material results in heat flow

=
Conduction contact, Convection- transport, Radiation - light

## Reread, Review and Reinforce concepts and techniques of Chapter 16

Examples 16.1: Specific Heat: waiting to Shower
Examples 16.2: Finding the Equilibrium temperature: Cooling Down
Examples 16.3, 16.5, 16.6: Conduction, Radiation and Thermal Energy Balance
GOT IT 16.1, 16.2, 16.3 and Green House effect application

## Thermal Behaviour of Matter

Gases: Ideal Gas Law
Gases: The Kinetic Theory of Gases
Phase Changes
Thermal Expansion
BIG PICTURE: Matter responds to heating in a variety of ways in addition to just
changing its temperature. Other responses include phase changes and changing
volume and/or pressure. The ideal gas is a simple way to tie macroscopic bulk
quantities to the microscopic interactions of Newtonian mechanics, culminating in
the proof that Temperature is a measure if the average molecular kinetic energy.

Gases

## Gases are simple to understand as they molecules are far apart

and rarely interact. Explaining their behaviour is relatively
straightforward. Empirically we can vary the properties of a
gas to see how they change and create the equation of state.

## Ideal Gases Law

=

Piston-Cylinder
System

Chemist version
= number of moles
= 8.314 1 1

Physicist version
= number of molecules
= 1.38 1023 1

Ideal Gas Law is the equation of state which describes how the
properties of gases are related. Most gases follow this law and
only depart when interactions become strong (extremely high
pressures and extremely low temperatures)

## a) If a 2.0 of an ideal gas are initially at temperature 250 and

pressure 1.5 , whats the gas volume ? b) The pressure is now
increased to 4.0 , and the gas volume drops to half its initial
value. Whats the new temperature ?

Interpret

Evaluate

a) =

Develop
a) = ,

b)

b)

= 0.0273

1
4.0

2 250
=
=

1.5

Assess

= 333

## 1. Monotonic gas with negligible size and no internal structure

2. Atoms only have KE and no long range forces
3. Atoms have random velocities

## Why do gases obey such a simple equation of state ?

Newton + a few simple assumptions can answer.

N gas atoms

= =

Newtons 2nd law

N gas atoms

## 1. Total average force sum over N

2. Multiply by N/N

F
p= =
A
mN
p=
V

## Average of the squares of the velocities

2
m
v
xi

AL
2
v
xi

m v xi2
V

mN 2
=
vx
V

2
v x2 = (v x21 + v x22 + ....v xN
)/ N

## Kinetic theory of gases

N gas atoms

mN 2
p=
vx
V
1. All directions random
2. Make pV subject

v x2 = v y2 = v z2

v 2 = v x2 + v y2 + v z2 = 3 v x2

2 1 2
p V = N ( mv )
3 2

## Temperature measures the average kinetic

energy associated with random translational
motion of an atom

p V = N k BT
1 2 3
m v = k BT
2
2

## Find the average kinetic energy of a molecule of air at room

temperature ( = 20) and determine the speed of a nitrogen
molecule (2 ) with this energy. (1 = 1.66 1027 )

1 2 3
m v = k BT
2
2

## Molecular Energy and Speed

1.E+04

Sun (~6000K)

1.E+03

Temperature (Kelvin)

vthermal

3k BT
=
m

Ice (273K)
Liquid Nitrogen (77K)

1.E+02
1.E+01

1.E+00
1.E-01

1.E-02
1.E-03
1.E-04
1.E-05

## Laser cooling (10K)

1.E-06

1.E-01

1.E+00

Evaporative
cooling
World record (50m/s, 450pK)

1.E+01

1.E+02

Velocity (m/s)

1.E+03

1.E+04

Phase Changes
eg. adding heat to ice, initially with T=-20 C at 1 atm.

T (C)
100

ice

heat of
vaporization Lv.

heat of
fusion Lf.
ice +
water

water

water
+
steam

steam

Q (Heat added)

The energy per unit mass to change a phase is called the latent
heat of transformation . For solid-liquid change its heat of
fusion , for liquid-gas change its heat of vaporisation .

Phase Changes

## PHYSCAST Heating with a phase change

A bowl contains 16 of punch (essentially water) at a warm 25 . What is
the minimum amount of ice at 0 needed to cool the punch to 0 .

Interpret

=
=

Evaluate

## Heat removed from water

= 0

Develop

1 = 1 ( )

1 = 16 4184 (0 25)

1 = 1.67 106

## = Heat added to ice to melt it only

2 = 2

1
1.67 106
2 =
=

334 103 /
Assess

2 = 5
1 ( )
2 =

PHYSCAST calorlimetry
A 75 ice cube at 3 is placed in a glass of water (0.20 at
= 20 ). At equilibrium, how much ice remains unmelted (if
any)? What is the final temperature of the drink ?
-ive sign : energy lost
Interpret
Evaluate
Energy released by cooling water, Q1
Q1 = 0.2 4184 20 = 16736 J
Energy absorbed by heating of ice, Q2
Energy absorbed by melting ice, Q3
If Q1 < Q2+Q3 then some ice is left

Q1 = m c T cw = 4184 J/kg C
Q2 = m c T cice = 2100 J/kg C
Q3 = L f m

Lf = 3.33

Develop

105

J/kg

## Q1 + Q2 = energy left to melt ice

16236
m=
= 49 g mice = 26 g
5
3.33 10

## Calorimetry with Phase Changes (really just conservation of energy) = . Take

care to account for all energies associated with temperature changes =
and with phase changes = . Note for phases must add sign in (+ s to l, - l to s)

Thermal Expansion
Ideal Gas ( ) = ( )

## Heat can change temperature, phase and volume.

Thermal Expansion
Coefficent of linear expansion =

## Often only care about the change in 1 dimension or

looking at long thin objects (railway).

## Chapter 17 Thermal Behaviour of Matter

Summary

The ideal gas law can be applied to most problems (with gases)
Know the chemist and physicist version (moles and molecules)
Only temperature dictates a molecules thermal speed
Calorlimetry is conservation of thermal energy

You put in the sign in manually for phase changes depending on direction

## Incompressible is an approximation, real things change their volume (slightly)

Reread, Review and Reinforce concepts and techniques of Chapter 17
Examples 17.2: Molecular Energy and Speed
Examples 17.3: The Heat of Fusion: Meltdown
Examples 17.4: Heat and Phase Change: Enough Ice
Examples 17.5: Thermal Expansion: Spilled Gasoline

## Heat, Work and the 1st law of Thermodynamics

The 1st Law of Thermodynamics
Thermodynamic Processes
Work and Volume Change
Isothermal Processes
Isovolumetric Processes
Isobaric Processes
Cyclical Processes
BIG PICTURE: Conservation of energy is now expanded to include heat. The
expanded statement is the first law of thermodynamics which relates the change of
a systems internal energy to the heat flowing into the system and the work done by
the system. We use diagrams along with the ideal gas law to describe
graphically basic thermodynamic proccesses.

## 1st Law of Thermodynamics

= internal energy ( )

= +

## + work done on the system

work done by the system

## The change of a closed systems internal energy depends only

on the net heat added to the system and the net work done on
the system, independent of the process.

Thermodynamic Processes

2
1

## fix N defines unique T

quasi-static (reversible)
process keeps water and
gas in equilibrium

## Work and Volume Change

How does the work done on the gas relate to volume ?
Gas exerts force on piston

= =

## work done on the gas, volume decreases.

The work done on the gas
during a volume change

= =
1

## Work and Volume Change

+ Work done by gas
increase volume
- Work done on gas
increase volume

=
=
2

## Graphical Interpretation of Work done

=
on gas: negative Area under curve
1

## Isothermal Processes (const T)

Isotherm
line of constant Temperature

=?
=

2
1
= =
= ln
1
1
1

Interpret
= 0 : Isothermal

U = 0, Q = W
Develop

25m

p2 = 1 atm
4
3
V2 = r2
3

Evaluate

V2
W = p dV = nRT ln
V1
V1
V2

nRT
nRT
V2 =
V1 =
p1V1 = nRT
p2
p1
V2 nRT p1
=
V1
p2 nRT

p1 3.5
=
=
= 3.5
p2
1

p1 = 3.5 atm
4
3
W = 3.5 101.3 103 2.110 6 ln (3.5)
V1 = r1
3
Assess
= 0.93 J
= 2.110 6 m 3

Adiabatic Processes

## Ideal gas law requires that

the temperature decreases
faster than an isotherm.

not examinable

## Adiabatic processes are when no heat flows between a system

and its environment. Examples include fast processes like
ignition in an engine or systems with perfect thermal
insulation. = and thus = .

Cyclical Processes

## In a cyclical process (engines etc.) the system periodically

returns to the same thermodynamic state. Thus over the
course of one cycle the change to the internal energy is
=_________. Work done and Heat added are _________________.

Past Exam Q: An ideal gas has an initial state, A, with volume 2.4 103 3,
temperature of 30 and a pressure of 2.0 . It is heated isovolumetrically to
state B which has a pressure of 4.0 . It is then cooled isobarically to state C
which has a volume of 1.2 103 3. Finally, the volume is increased isothermally
until the original volume is reached.
(i) Sketch a PV diagram for the above sequence, clearly indicating the P and V
values for states A, B, and C, and the paths between them.

4 atm

2 atm

1.2 10 3

= 30
V
2.4 10 3

Calculate the work done by the gas during each of the state changes:
(I) A B
Interpret: Work done by gas is + area under PV curve
(II) B C
(III) C A
Evaluate: (I) Isometric change, V=0 no work is done, W = 0 J
(II) Isobaric change, W = PV

P
4 atm

Assess !

W = P(V f Vi )

W = 486 J

PV = nRT

## (III) Isothermal change, const T + ideal gas.

2 atm

A
T = 30o C = 303K

V
1.2 10 3 2.4 10 3

Vf
1
W = PdV = nRT dV = nRT ln( )
V
Vi
VA
= PAVA ln( ) = 4.8 101.3 ln(2)
VC
= +337 J

(iii) For change (III), going from C to A, use the First Law of
Thermodynamics or otherwise to find the heat added to the gas.

W = +337 J

## Interpret: Isothermal process, const T, U=0.

P
4 atm

Evaluate: U = Q W = 0
Q =W
net heat added to gas = Q = 337 J

2 atm

A
T = 30o C = 303K

V
1.2 10 3 2.4 10 3

Summary

## 1st law of thermodynamics: change in temp = heat added + work done on

Work done on = - Work done by
A system is what you define it to be, it just has to be closed.
A single point on a diagram has a well defined temperature
Isothermal=cost , Isovolumetric=const , Isobaric=const .

Work done on a gas is path specific and = minus the area under a curve.
Reread, Review and Reinforce concepts and techniques of Chapter 18
Examples 18.1: The 1st law of Thermodynamics: Thermal Polution