5

phys 241 Δ𝑇 = Δ𝑇𝐶 = Δ𝑇𝐹

9
Thermodynamics

CH1
Temperature
𝑇 = 𝑇𝐶 +273.15
9
𝑇𝐹 = 𝑇𝐶 + 32
5
 Important concepts
System types
1. system , surrounding, and boundaries
Open System
System: a particular part of the universe
Exchange Mass Heat
Surroundings: the rest of the universe
Boundary: separates the system and the surroundings (real or
imaginary)(rigid or movable)
piston

Usually Gas system Closed System

thermodynamics laws are Exchange Heat
applicable to all forms of matter but
it is easier to deal with and
understand when the system is gas Gas
system

Isolated System
homogenous system: its properties are uniform throughout such a
system consists of a single phase (water or well mixed coffee in a cup)
heterogeneous system: a system contains more than one phase
(water+ice or oil+water at equilibrium in a cup)
 Important concepts piston

2. Intensive and extensive variables

Intensive variables: independent of size or quantity (e.g. P, T)
Extensive variables: dependent on size or quantity (e.g. V, n # of moles,
U internal energy, S entropy)

Gas
system

PVTn
P0 V0 T0 n0 P0 V0 T0 n0 P0 2V0 T0 2n0
Note: the ratio of two extensive
variables is an intensive variable
e.g. density and molar volume
 Important concepts
3. equilibrium state
The state in which all the bulk physical properties of the system are uniform throughout the system and do not
change with time

After SOME time

Equilibrium Equilibrium
state state

Thermodynamic deals primarily with equilibrium states

 Important concepts Equivalent terminology for state variables
thermodynamic variables
thermodynamic coordinates
4. State variables and process variables
State variables values is dependent on and measurable at equilibrium states (path independent) (e.g. P,T,V,U,S)
Process variables values is dependent on the path from one equilibrium state to another (path dependent) (e.g. work W,
heat Q)

final

initial

• elevation depends only on initial and final points

(path independent)
• Length of trail depends on the path (path • Vf and Pf don’t depend on the path
dependent) • w and Q are different for different paths
 Important concepts piston

5. Equation of state
An equation relating state variables at equilibrium
for ideal gas
(no intermolecular forces and molecules volume )
𝑃𝑉 =𝑛𝑅𝑇 (empirical law)
specifying these equilibrium values of a pair of independent variables (e.g. P and V),
together with the mass, defines the system. And fixes all the macroscopic or bulk Gas system
properties of the gas(e.g. the thermal conductivity, viscosity, internal energy, entropy, …)
which can be driven from the pair of independent variables PVTn
𝑃𝑓 = 3x105 (𝑃𝑎)
𝑉𝑓 = 0.002 (𝑚3 )
𝑇f =? (K)
𝑛 =? (𝑚𝑜𝑙) Instead of the mass we usually use the amount of
𝑅 = 8.314 (
𝐽
)
substance; it is the number of entities (N) (atoms,
𝐾 𝑚𝑜𝑙 molecules, …) expressed in terms of moles (n) where:
𝑃𝑖 = 1x105 (𝑃𝑎) 𝑁
𝑉𝑖 = 0.001 (𝑚3 ) 𝑛=
𝑁𝐴
𝑇i = 300 (K)
𝑛 =? (𝑚𝑜𝑙) 𝑁𝐴 is the Avogadro number = 6.022 x 1023 entity/mol
𝐽
𝑅 = 8.314 ( )
𝐾 𝑚𝑜𝑙
 ideal gas law
1
In 1662, Robert Boyle found 𝑉1 α when T and n are fixed
𝑃1
𝑛1 𝑇1
In 1780s, Jacques Charles found 𝑉1 α 𝑇1 when P and n are fixed 𝑉1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑃1
in 1811, Amedeo Avogadro proposed 𝑉1 α 𝑛1 when T and P are fixed

𝑉𝑃 = 𝑅𝑛𝑇

𝑉𝑃 = 𝑘𝑁𝑇
 gas molecule K.E. and thermal energy
Δ𝑉𝑥
𝐹𝑥,𝑎𝑣𝑔 𝑚 𝑣𝑥
Pavg = = Δ𝑡
𝐴 𝐴 𝑣

2𝐿 𝐿
Δ𝑉𝑥 = 2𝑣𝑥 Δ𝑡 =
𝑣𝑥 1 1
𝑘𝑇 = 𝑚𝑣𝑥2
𝑚𝑣𝑥2 𝑚𝑣𝑥2 2 2
Pavg = = 1 1 1
𝐴𝐿 𝑉 𝐾𝑡𝑟𝑎𝑛𝑠 = 𝑚𝑣𝑥 + 𝑚𝑣𝑦 + 𝑚𝑣𝑧2
2 2
2 2 2
1 1 1 3
𝑃𝑉 = 𝑁𝑚𝑣𝑥2 𝐾𝑡𝑟𝑎𝑛𝑠 = 𝑘𝑇 + 𝑘𝑇 + 𝑘𝑇 = 𝑘𝑇
2 2 2 2
𝑉𝑃 = 𝑘𝑁𝑇 𝟑
𝑁𝑘𝑇 = 𝑁𝑚𝑣𝑥2 𝑲𝒕𝒓𝒂𝒏𝒔 = 𝒌𝑻
𝟐
 0th law and temperature
0th law

“If each of two systems is in thermal

equilibrium with a third , they are in thermal
equilibrium with one another”

Temperature
“The temperature of a system is a property that determines whether or not that system is
in thermal equilibrium with other systems”

thermal equilibrium mechanical equilibrium P1 P2

T P T1 T2
 Scales of Temperature
For numerical values of different temperatures we need to:
1- choose a system (Hg in glass, or platinum wire)
2- select a physical property that is easy to be measured and varies with
temperature (length of Hg column, electrical resistance of platinum wire)
3- select a reference temperature (triple point of water = 273.16 [reason for this
number will be explained later])

𝑇𝑋 = 𝑐 𝑋 c is a constant (linearity assumption)

𝑇𝑋
273.16
𝑇𝑋 = 𝑋
𝑋𝑇𝑃
Two main issues with different thermometers:
1- different thermometers (with different physical properties ) 273.16 273.16
𝑠𝑙𝑜𝑝𝑒 =
𝑋𝑇𝑃
give slightly different readings (not 100% linear)
2- physical property values should vanish for Tx= 0 and this is 𝑋
usually not the case as these properties don’t go to zero 𝑋𝑇𝑃
Why triple points?

This triple point occurs at a

temperature of 0.01oC and a
pressure of 4.58 mm of mercury
the temperature of water at the
triple point was 273.16 K

the ice and steam points are experimentally difficult to duplicate (depend on atmospheric pressure)
The absolute temperature scale is based on two new fixed points:
1. absolute zero
2. triple point of water (which is the single combination of temperature and pressure at which
liquid water, gaseous water, and ice coexist in equilibrium)
 the Gas Scale of Temperature
The constant volume gas The steam point as a function of the mass of gas
thermometer provides a used in a constant-volume gas thermometer
procedure for obtaining a unique
temperature independent of the
thermometric material as we will
see below, and therefore it is Why?
used as a standard
thermometer

1. Have water in the three phases at equilibrium TP

2. Readjust the open tube height so the gas volume doesn’t change
3. measure PTP from: 𝑃 = 𝑃0 + ρ𝑔ℎ (thermometric parameter)
4. Use a similar relation: 𝑃 Ideal gas scale:
𝑇 = 273.16
𝑃𝑇𝑃 𝑃
5. Put the gas in any environment and measure the pressure as in (3.) 𝑇 = 273.16 lim
𝑃𝑇𝑃 →0 𝑃𝑇𝑃
and use equation in (4.) to find T
 The absolute zero and the Kelvin scale

• All different gas thermometers (with diluted gas) when

approach -273.15 oC, their pressure approaches 0 𝑜
• This temperature is called the absolute zero and is the 𝑡 𝐶 = 𝑇 𝐾 − 273.15
zero point of the Kelvin scale (ideal gas scale)