Introduction

What we know: behavior of matter

à EOS
What we are ready to study: behavior of energy à
LAWs of TD

MACROscopic Statistical MICROscopic

Thermodynamics
description (PChem III) description

Thermodynamics Quantum Mechanics

(PChem I) (PChem II)
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 1
 Introduction
surroundings
Matter
system Open system
Energy

Matter
Matter

Closed system Energy

Isolated system
Energy
Earth Energy OUT

Solar Energy IN

CH3510 - PChem I Teaching Material by L. Valenzano-Slough 2

 Work
Any memory from Physics?
!
1D: A force F acts on a object that is displaced by dx

The infinitesimal amount of work done

on the object by the force is
dw º Fx dx
Fx = component of the force in the direction of the
displacement
3D: dw º Fx dx + Fy dy + Fz dz
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 3
 Work
How do I get to the finite amount of work done?
$& Fx = const $&
dw º Fx dx ! = # '$ () ! = '$ # () = '$ ()+ − )- )
$% $%

1D: ! = '$ ∆)
3D: ! = '(∆) + ∆y + ∆z) '$ = '3 = '4 = 56789 = '

Units?
[!] = ['$ ∆)] = 1= > 1? = 1@A > ? > 8 B+ > ? =
=1@A > ?+ 8 B+ = 1C
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 4
 Work
! ! ! !
w = F × s = F s cosJ = Fs cosJ
! !
F ¹0 F ¹0

! !
s =0 s >0

w=0 w>0
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 5
 Work
! ! ! !
w = F × s = F s cosJ = Fs cosJ
Things to remember about work:
1) It’s not a vector (no direction, no verse!)
2) It’s a scalar (yes magnitude!)
*Which other way of
3) It has the unit of energy (Joule) transferring energy
we mentioned?
4) It’s a way of transferring energy*
For our purposes (and for the time being):
work is mainly related to a change of volume
of the system and is “mechanical PV work”

w µ DV
Consistent with:
! = #(∆& + ∆y + ∆z)
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 6
 Mechanical PV Work
l

Fext Fint
!"#$ = !&'$ = !
External
Pressure Equal opposing forces act on the piston:
Pext System (Pint, T, V) àmechanical equilibrium
à reversible mechanical process
x b (expansion/compression)
Piston (part of the surroundings)

Fx = component of the force applied by the piston on the system

dw = Fx dx = amount of work done by the surroundings on the system
F = magnitude of the force applied by the system on the piston

Newton’s Third Law (action = reaction) à Fx = F = PA

à dw = PAdx
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 7
 Mechanical PV Work
l
dw = PAdx
External Fext Fint
Pressure A = cross-sectional area of the system
Pext
System (Pint, T, V) l = b – x = length of the system

x b V = lA = (b – x)A = volume of the system

Piston (part of the surroundings)

dV = d ( Ab - Ax) = Adb + bdA - Adx - xdA = - Adx

dx = - dV
A dw = PA - dV ( A
)
PV (mechanical) work for a closed system
dwrev = - PdV undergoing a reversible process
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 8
 Mechanical PV Work
dwrev = - PdV !"#$% = −()*
dV < 0 dV > 0
Compression of the system Expansion of the system
!"#$% > 0 !"#$% < 0
The surroundings is doing work The system is doing work on
on the system! the surroundings!

The work done by the The work done by the system

surroundings increases the decreases the energy of the
energy of the system! system itself!

The system gains energy The system loses energy

CH3510 - PChem I Teaching Material by L. Valenzano-Slough 9
 Mechanical PV Work
Pext Pext
123'4 = −%6!
%'() = %"+) = % = ,-./0

!" < !$
%" > %$
!" , %" !$ , %$

State 1: External pressure is applied to the system

State 2: The system infinitesimally expands against Pext
à The system does work on the surroundings

The system loses energy in form of work !

CH3510 - PChem I Teaching Material by L. Valenzano-Slough 10
 Mechanical PV Work
In general (no reversible process):
Vf

!" = −%&'( )* w = - ò Pext dV

Vi

Pext = const
Vf

w = - Pext ò dV = - Pext V V = - Pext (V f - Vi ) = - Pext DV

Vf
i
Vi

w = - Pext DV

CH3510 - PChem I Teaching Material by L. Valenzano-Slough 11

 Mechanical PV Work
From a more general stand point (no reversible process):
%&'( = +,-./
!" = −%&'( )* " = −%&'( ∆*
">0 "<0
Work done by Work done by system
surroundings on system on surroundings
(system gains energy) (system loses energy)

Work done by the Work done by the system

surroundings increases the decreases the energy of
energy of the system the system
The sign refers to the “system point of view”
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 12
 Mechanical PV Work

!" = −%&'( )* Which units do we use for w?

Work is a way of transferring energy (SI) à Joule (J)

At the same time P à atm, V à L

so that w à atm·L

1 atm·L = 101.32 J
Checking the units in SI
Pa ´ m3 = N/m2 ´ m3 = N ´ m = J
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 13