ER CH5-Student 2023

CHEM 2011
CH 5: ENTROPY & 2nd LAW

CHEM 2011
5.1-5.10
* Some concepts are covered in more detail than
in the book in order to include review material
from first year, and a more detailed microscopic
picture of entropy is presented in the notes.
CHEM 2011
CHAPTER 5
End of Chapter questions for practice:
Questions: 1, 2, 5, 7, 8, 9, 12, 13, 15, 17, 18, 19, 20
Problems: 2, 3, 4, 5*, 8, 9, 12, 13, 16, 17, 19, 21, 32, 33, 35, 38**, 39, 41
*typo in a), but right final answer

**typo in b) for wda, but final answer correct
CHEM 2011
The greater the degree of

randomness or disorder in a
system, the greater its
entropy
Department of Entropy
CHEM 2011
Direction of
A spontaneous change is one that spontaneous change
occurs without a continuous input water ice
of energy from outside the system.
Easy to predict in the physical world:
Water flows and balls roll downhill

spontaneously to reach lower Direction of
potential energy in the presence of spontaneous change
gravity
Sugar cube above Sugar cube dissolved

a coffee cup in a coffee cup
CHEM 2011
A catalyst can increase the rate of a

spontaneous process.
A catalyst cannot do so for a non-

spontaneous process.
Non-spontaneous processes are not

IMPOSSIBLE, they require the input
of external energy or coupling to a
more spontaneous reaction to
proceed
Some spontaneous processes can be very slow

CHEM 2011
Free expansion of gas

Increase in entropy
Free compression of gas

Decrease in entropy
HIGH TEMP LOW TEMP Increase in entropy

EQUAL TEMP
Decrease in entropy
CHEM 2011
Tennis ball bouncing: would it make sense to draw the arrows in
the other direction?
Potential energy represents nondispered energy, thermal

energy represent dispersed energy
CHEM 2011
• Each time the ball hits the floor some of its KE is dissipated among
molecules in the floor.
• Floor becomes warmer
• Eventually ball comes to rest: all of its KE transferred to the floor.
Inelastic Collisions Conversion of PE and KE into internal energy

CHEM 2011
CH 5: ENTROPY & 2nd LAW NO WAY – GIVEN THE RANDOM
NATURE OF MOLECULAR
MOTION!
• For this process to occur, the

ball needs to absorb sufficient
energy from the floor
The magnitude of energy required to have a ball at rest
• The thermal energy of the
on the floor suddenly start bouncing into air would be
floor is random molecular
equivalent to having 6.0  1023 molecules aligned and
motion
vibrating in phase in the upwards direction.
• The amount of energy needed
to raise the ball would require Calculating W for complex systems is too difficult. Entropy changes can be
all molecules within the floor measured from changes of other thermodynamic quantities such as q (heat)
to line up and vibrate in 𝒒𝒓𝒆𝒗
phase with one another. 𝑺=
𝑻
CHEM 2011
How do we know the
direction of spontaneity
of chemical reactions we
A process occurs spontaneously in only one are not familiar with?
direction. The reverse cannot occur
spontaneously under the same conditions.
Why doesn’t the coffee

suck out all the energy
out of the cold water?
FIRST LAW OF THERMODYNAMICS

✓ accounts for energy
X does not predict direction of spontaneous energy transfer
IF THIS WAS NOT TRUE NOTHING So we need the 2nd Law….this Law relies on something called
Entropy (S)…..
WOULD EVER OCCUR!
CHEM 2011
focus on large-scale properties of matter focus on the concept of molecules
Position, velocity, mass, describing the

microscopic motion of gas molecules
CHEM 2011
STATE FUNCTION
UNITS: J/K
is a thermodynamic quantity that is a measure of how
dispersed the energy of a system is among the different
possible ways that the system can contain energy.
If we consider both the system and the 𝑺 = 𝒌𝒃 𝒍𝒏𝑾 Entropy has units of J K-1
surroundings, we find that all real processes
occur spontaneously in the direction that W number of possible arrangements of position and
increases the entropy of the universe. energy of molecules (microstates, unitless)
kb Boltzmann constant = 1.38 × 10−23 J/K

ΔSuniv = ΔSsys + ΔSsurr > 0
1
2
CHEM 2011
CHThe
5: ENTROPY & 2nd LAW
key to understanding entropy is to understand W. How can the energy of a system be
distributed in different ways, while the total energy is kept constant?
SOLIDS
• 3D array of coupled
harmonic oscillators
CHEM 2011
𝑺 = 𝒌𝒃 𝒍𝒏𝑾
gas expansion heat transfer from hotter to colder object
Macrostate
Gas with constant
T, P, and V
The macrostate is the

overall state of a
system as defined by a
given set of
conditions.
CHEM 2011
Consider the expansion of an ideal gas from a flask, through some tubing connecting it to an
EXAMPLE
evacuated flask when a valve is opened.
1. When the valve is opened the gas expands spontaneously
2. The energy levels for each molecule move closer together and increase in number
3. The number of microstates for the system increase and so does entropy
LOWER S HIGHER S
ΔS > 0
When entropy increases during a chemical or physical process, then, it has a positive value for the change
in entropy:
spontaneous processes have a positive ∆𝑺
∆𝑺 = 𝑺𝒇𝒊𝒏𝒂𝒍 − 𝑺𝒊𝒏𝒊𝒕𝒊𝒂𝒍 according to the 2nd Law of
Thermodynamics
CHEM 2011
A microstate is a single possible

arrangement of position and
kinetic energy of molecules.
Entropy is a measure of how many
microstates are associated with a
particular macroscopic state.
The macrostate with the highest
entropy also has the greatest
When the stopcock opens, the number of microstates is
dispersal of energy.
W = 2n, where n is the number of particles.
CHEM 2011
If you had a set-up as shown below, how many microstates
would you have
a) when the stopcock is closed?
b) when the stopcock is open?
C
D
A) Closed: 1, Open: 4
B) Closed: 4, Open: 8
C) Closed: 3, Open: 4
D) Closed: 1, Open: 16
E) Closed: 4, Open: 16
CHEM 2011
EXAMPLE
Assume we have a solid system with four atoms and a total energy of 1E.
How many different ways could you distribute that energy among the 4
different atoms?
If there are N atoms and the total energy is qE, then the number of
microstates is given by
According to quantum
mechanics, atoms in a crystal 𝒒+𝑵−𝟏 !
have energies 0, 1E, 2E, 3E, … 𝑾 𝑵, 𝒒 =
𝒒! 𝑵 − 𝟏 !
How many different ways the
total energy can be subdivided
among all the atoms = W N=4 q=1
NUMBER OF MICROSTATES 𝟏+𝟒−𝟏 ! 𝟒! 𝟒×𝟑×𝟐×𝟏
(multiplicity) 𝑾 𝟒, 𝟏 = = =
𝟏! 𝟒−𝟏 ! 𝟏!𝟑! 𝟏× 𝟑×𝟐×𝟏
=𝟒
CHEM 2011
A hot and a cold bar, each made up of 4

atoms, are pushed together. What will
happen?
If the cold bar has 1 quantum of energy HINT: when evaluating entropy change, ΔS will be related to the possible
and the hot bar has 5 quanta of energy in accessible microstates.
the initial state, show that heat transfer is
spontaneous by calculating ΔSuniverse for
the process. 𝜟𝑺 = 𝒌𝒃 𝒍𝒏𝑾𝒇𝒊𝒏𝒂𝒍 -𝒌𝒃 𝒍𝒏𝑾𝒊𝒏𝒊𝒕𝒊𝒂𝒍
CHEM 2011
4 4
1 3
4 20
If there are N atoms and

the total energy is qE, then
the number of microstates 4 4
is given by
5 3
𝒒+𝑵−𝟏 !
𝑾 𝑵, 𝒒 = 56 20
𝒒! 𝑵 − 𝟏 !
CHEM 2011
𝜟𝑺 = 𝒌𝒃 𝒍𝒏𝑾𝒇𝒊𝒏𝒂𝒍 -𝒌𝒃 𝒍𝒏𝑾𝒊𝒏𝒊𝒕𝒊𝒂𝒍
kb= 1.38 × 10−23 J/K
∆𝑺𝒔𝒚𝒔 = 𝒌𝒃 𝒍𝒏𝟐𝟎 − 𝒌𝒃 𝒍𝒏𝟒 = 𝟐. 𝟐𝟐 × 𝟏𝟎−𝟐𝟑 𝑱/𝑲
SYSTEM
𝜟𝑺𝒔𝒖𝒓𝒓 = 𝒌𝒃 𝒍𝒏𝟐𝟎 − 𝒌𝒃 𝒍𝒏𝟓𝟔 = −𝟏. 𝟒𝟐 × 𝟏𝟎−𝟐𝟑 𝑱/𝑲
SURROUNDINGS
Heat transfer from a hot object to a 𝜟𝑺𝒖𝒏𝒊𝒗𝒆𝒓𝒔𝒆 = 𝜟𝑺𝒔𝒚𝒔 + 𝜟𝑺𝒔𝒖𝒓𝒓 = 𝟎. 𝟖𝟎 × 𝟏𝟎−𝟐𝟑 𝑱/𝑲
cold object is SPONTANEOUS. UNIVERSE
CHEM 2011
What would be the ΔSuniverse if heat was transferred from the cold rod
(1 E initially) to the hot rod (5 E initially) and their total energies in the
final state are 0E, for the cold rod, and 6E for the hot rod.
𝐀) 𝚫𝐒𝐮𝐧𝐢𝐯𝐞𝐫𝐬𝐞 < 𝟎
B) 𝚫𝐒𝐮𝐧𝐢𝐯𝐞𝐫𝐬𝐞 = 𝟎
𝐂) 𝚫𝐒𝐮𝐧𝐢𝐯𝐞𝐫𝐬𝐞 > 𝟎
CHEM 2011
What would be the ΔSuniverse if heat was transferred from the cold rod (1 E initially) to
𝒒+𝑵−𝟏 ! the hot rod (5 E initially) and their total energies in the final state are 0E, for the cold
𝑾 𝑵, 𝒒 =
𝒒! 𝑵 − 𝟏 ! rod, and 6E for the hot rod.
𝜟𝑺𝒖𝒏𝒊𝒗𝒆𝒓𝒔𝒆 = −𝟏. 𝟑𝟓 × 𝟏𝟎−𝟐𝟑 𝑱/𝑲

CHEM 2011
Allowed energy levels for a He

atom in a one-dimensional box.
Box length is 10.0 nm in (a) and
8.00 nm in (b). The length of the
chain of circles on each energy
level gives the probability that
each energy level is occupied.
One circle corresponds to a
probability of 0.01. The
connecting lines between the
boxes show how the energy
levels change as the box
length increases from 8.00 nm
to 10.0 nm
CHEM 2011
Probabilities for a He atom of

occupying the allowed energy
levels in a one-dimensional box.
Energy levels are for (a) 0.200 K
and (b) 0.300 K. Box lengths for
both diagrams are 10.0 nm. The
length of the chain of circles on
each energy level is proportional
to the probability that each
energy level is occupied. One
circle corresponds to a
probability of 0.01
CHEM 2011
VOLUME = V1 VOLUME = V2
• For a cylinder containing He atoms the probability of finding any one atom in V 2
(the entire volume of the cylinder) = 1
• The probability of finding an He atom in ½ the volume (i.e. V1) = ½
• The probability of finding two He atoms in V1 is (½)(½) or ¼
the probability = W = ( ½ )N where N is no. of atoms

…so as N increases the probability of finding all atoms in V1 decreases
CHEM 2011
VOLUME = V1 VOLUME = V2
INITIAL STATE (LEAST PROBABLE): all atoms compressed in V1

FINAL STATE (MOST PROBABLE): all atoms evenly distributed over entire V2
…spontaneous change occurs from state of low probability of occurring

to state of maximum probability
CHEM 2011
We can now express enthalpy as being proportional to probability:
S = kBW kB = Boltzmann constant = 1.381  10-23J/K
but this equation is actually INCORRECT….
BOLTZMANN EQ. as W increases to W2…S increases to 2S

remember lnW2 = 2lnW
S = kB lnW
INITIAL STATE FINAL STATE

S1 = kB lnW1 S2 = kB lnW2
ENTROPY is a state function, so it is path independent.

 W2 
S = S2 − S1 = kB ln 
 W1 
CHEM 2011 STATISTICAL DEFINITION OF ENTROPY
Q
Q: What is the probability of a gas expanding from V1 to V2 ? (isothermal expansion)
PROBABILITY OF EACH STATE: W1 = (CV1 )N W2 = (CV2 )N
N
 (CV2 ) N
 V2 
S = S2 − S1 = kB ln  = kB ln 
N 
 (CV1 )   V1  Where kBNA = R
N  V2   V2 
S = R ln  = nR ln 
NA  V1   V1 
Condition: This equation holds for an isothermal expansion, as entropy is affected by changes in temperature.
Entropy is a state function, so it does not matter how the expansion happened!
CHEM 2011 Calculate the change in entropy when the volume of 85.0 g of CO initially at 298 K
CH 5: ENTROPY & 2nd LAW and 1.00 bar increases by a factor of three in an isothermal reversible expansion
INITIAL STATE FINAL STATE  V2 

S = nR ln 
V1 V2 = 3V1  V1 
(85 g ) (3  V1 )
V2
ΔS = n R ln =  (8.314472 J mol−1 −1
K )  ln = 27.7 J K −1
V1 (28 g mol-1 ) (V1 )

Now, estimate the probability that the gas will contract spontaneously from the final volume to the initial volume.
 W1 
S = kB ln  (since the process is now defined as 2 1)
 W2 
Spontaneous contraction will be accompanied by a decrease in entropy by 27.7 J/K
 W1   W1  −2.091024
− 27.7 J/K = ( 1.381  10 - 23
J/K) ln    = e
 W2   W2 
CHEM 2011
nA , VA nB , VB n = nA + nB , V = VA + VB
P, T P, T P, T
To calculate entropy of mixing, ΔS, treat the process as two separate, isothermal gas expansions.
 VA + VB   VA + VB 
SA = nAR ln  SB = nBR ln 
 VA   VB 
 VA + VB   VA + VB 
 mix S = SA + SB = nAR ln  + nBR ln 
 VA   VB 
CHEM 2011
 VA + VB   VA + VB 
 mix S = SA + SB = nAR ln  + nBR ln 
 VA   VB 
Avogadro’s Law: V n at constant T and P, so
 nA + nB   nA + nB 
 mix S = nAR ln  + nBR ln 
 nA   nB 
 nA   nB 
 mix S = - nAR ln  − nBR ln 
 nA + nB   nA + nB 
 mix S = - R(nA ln  A + nB ln  B )
Since, χA and χB are mole fractions of A and B respectively and their values are <1, it follows that ΔmixS > 0
CHEM 2011
For isothermal expansion of an ideal gas:
V 
S = nR ln 2 
 V1 
Heat absorbed by an ideal gas in an isothermal expansion:
 V2 
qrev = nRT ln 
 V1 
qrev  V2 
So = nR ln 
T  V1 
This equation is true for any
qrev
Thus S = reversible process occurring
T at constant temperature
CHEM 2011 𝑑𝑞𝑟𝑒𝑣 = 𝑑𝑈 − 𝑑𝑤𝑟𝑒𝑣
Start from first law and note that q
and w are path-dependent
𝑛𝑅𝑇
= 𝐶𝑉 𝑇 𝑑𝑇 + 𝑃𝑑𝑉 = 𝐶𝑉 𝑇 𝑑𝑇 + 𝑑𝑉
𝑉
𝜕𝐶𝑉 𝑇 𝜕(𝑛𝑅 𝑇Τ𝑉 ) q is not a state function , and so

≠ the mixed second partial
𝜕𝑉 𝑇
𝜕𝑇 𝑉 derivatives are not equal
𝒅𝒒𝒓𝒆𝒗 𝑑𝑞𝑟𝑒𝑣 𝐶𝑉 𝑇 𝑛𝑅 Dividing both sides by T gives an

𝑺= = 𝑑𝑇 + 𝑑𝑉
𝑻 𝑇 𝑇 𝑉 exact differential
𝜕 𝐶𝑉 𝑇 Τ𝑇 𝜕(𝑛 𝑅 Τ𝑉 )
=
𝜕𝑉 𝑇
𝜕𝑇 𝑉
𝑇𝑓 𝑉𝑓
𝑑𝑞𝑟𝑒𝑣 𝐶𝑉 𝑇 𝑛𝑅 Change in entropy of an ideal gas
∆𝑆 𝑉, 𝑇 = න𝑑𝑆 = න =න 𝑑𝑇 + න 𝑑𝑉 undergoing change in V and T
𝑇 𝑇𝑖 𝑇 𝑉𝑖 𝑉
𝑇𝑓 𝑉𝑓 If CV is temperature independent, it
∆𝑆 𝑉, 𝑇 = 𝐶𝑉 𝑙𝑛 + 𝑛𝑅𝑙𝑛 can be removed from the integral.
𝑇𝑖 𝑉𝑖
CHEM 2011
dqreversible
S =  = ENTROPY
• Exchange dqrev for a term containing dT
• Integrate from Ti to Tf
T
Isothermal situation: qreversible = -wreversible = nRT ln Vf/Vi
Vf
d( nRT ln )
dqreversible Vi Vf
S =  = = nR ln
T T Vi
Change in T at constant V: qreversible = nCvdT

dqreversible nC dT T
S =  =  v = nC v ln f
T T Ti
Change in T at constant P: qreversible = nCPdT
dqreversible nC dT T
S =  =  P = nC P ln f
T T Ti
CHEM 2011
When a gas is first reversible compressed at constant
temperature, then heated at constant volume, the change in
entropy of the system is
A) positive
B) negative
C) It depends on the magnitude of the change in

entropy of the two steps
CHEM 2011
Vi Ti Vf Ti Vf Tf
Vi , Ti → Vf , T f
ΔS = n R ln Vf/Vi + nCv,mlnTf/Ti
Pi Ti P f Ti P f Tf
Ti , P i → Tf , P f
ΔS = - n R ln Pf/Pi + nCp,mlnTf/Ti
Add component under isothermal conditions due to P or V change and then

component due to T change.
CHEM 2011
Entropy in different situations we have thought about

qreversible
Process qreversible S =  T
Any cyclic process Depends 0 (state function)
Reversible adiabatic process 0  0
Reversible isothermal expansion or compression -wreversible = n R T ln Vf/Vi n R ln Vf/Vi
Reversible/irreversible change in T at constant V nCvdT nCvlnTf/Ti
Reversible/irreversible change in T at constant P nCpdT nCplnTf/Ti
Reversible and irreversible case must have same initial and final states
What happens if considering an irreversible process?
CRITICAL: ΔS must be calculated along a reversible path
CHEM 2011
One mole of N2 at 20.5°C and 6.00 bar undergoes a transformation to the state described by 145°C and 2.75
bar. Calculate ΔS if 2 3
CP,m T T −8 T
= 30.81 − 11.87  10−3 + 2.3968  10 −5 2 −1.0176  10
J mol −1 K−1 K K K3
TfTTf f
p
pfpff + n C CC
ΔS = n nRRlnln p++n nf p,m
− n R ln dT
p,m
ΔS ΔS==−− T
C
p,m
dTdT
ΔS = − n R lnpipii + nTiTTii TT dT
p f T p,m
pi T
( ((2.75 bar) ))
((8.314472J Jmol mol KK ) )) lnln ( 2.75 bar )
Ti
bar
) ) (8.314472
2.75
2.75bar
= − (
==−−(1(1mol1 mol
mol )  8.314472 J mol −1−−11 −1−−11
K  ln
= − (1 mol )  (8.314472 J mol −1 K −1 )  ln ((6.00
( 6.00
6.00bar bar) ))
bar

( 6.00 bar )
 TT3
2 22 3 33
T
−3−−33TT −5−−55TT 2
T −8−−88 T
30.81−−−11.87
30.81
30.81 11.87
11.87 101010 T+++2.3968 2.3968
2.3968 10 10  T−−−1.0176
10 1.0176
1.0176 10 10  T
10
418.15
418.15 KKK
−  −K3K
+  −  K 
    − 1.0176  10−8K K   TTT
  ddd JJJKK
418.15
   K 5 KK K
+++(1((11mol ) )) 418.15 30.81 11.87 10 2.3968 10
mol
mol
+ (1 mol293.65

 KK  K
K  
K    KKT
K K-1-1 -1
)293.65
293.65 K
TTT d K J K -1
T K 3 418.15 418.15KKK
 TT.T15K3 418.15 K -1-1-1
3 3 418.15
293.65 K
 T f 
-1   TfTf −5−−55TTT 2
2 22
((6.48
===( 6.486.48JJJKK K ) )+)++ln
-1-1
ln Txxx30.81
ln 30.81
30.81 −−11.8711.87
−11.87 1010 −3−−33TT
10 2
T
+.+3969
+2.3968
2.3968
2.3968 
 10 10−10 2 T
105 −−−1.0176
1.0176
  1010
1.0176
1.0176 − 8 10 −8−−88418
103  T JJJKKK
= ( 6.48 J K ) +(ln
−3 −3K T
KK + 2.3968  10TK K − 1.0176 T10)K K=
-1 T
30TiTi.i 81
f T − 11
 xln30.81 .−87  10 10
11.87 T+ − 5
−

K − 8

K 293.65
16.8
293.65KKK
JJKK-1-1
-1-1K  3 K 
293.65
 Ti -1-1-1  K -1 2
−1−−11 293.65K  293.65 K
((6.48
( 6.48
6.48JJJKK K )-1)+)++(10.89
-1-1-1
((10.89
10.89JJJKK K )-1)−)−−(1.48
((1.48
1.48JJJKK K )-1)+)++(1.06
-1-1
-1
((1.06
1.06JJJKK K )-1)−)−−(1.06
-1 -1
((1.06
1.06JJJKK K )-1)) === 16.8
-1
16.8
16.8JJJKK K −1
CHEM 2011
Consider entropy change for following processes: ΔS
Increasing volume of a gas n R ln Vf/Vi +

Compression of a gas n R ln Vf/Vi -
T increased at constant P nCplnTf/Ti +
T decreased at constant P nCplnTf/Ti -
CHEM 2011
IN ISOLATED SYSTEMS
ΔS > 0 for the spontaneous process direction
ΔS < 0 for the non spontaneous process direction
ΔS = 0 for a reversible process
Condition
System does not exchange energy with surroundings in the form of heat or work
Why?
Changes in the surroundings produce entropy changes in the surroundings
ΔSsystem + ΔSsurroundings >0

CHEM 2011
(1) CaCO3(s) CaO(s) + CO2(g) 

ΔSreaction = +160.5 J / K
(2) 2H2(g) + O2(g) 2H2O(l) 

ΔSreaction = −326.4 J / K
(3) N2(g) + O2(g) 2NO(g) 

ΔSreaction = +24.7 J / K
Consider the reaction to produce water (equation 2)….the entropy is negative

because the net number of gas molecules decrease and we are producing a liquid
from gases.
One would except that this reaction would not occur…
BUT don’t forget we have only considered the Entropy of the SYSTEM….what about
Entropy of the SURROUNDINGS?
CHEM 2011
SYSTEM
Besides the SYSTEM, we also have to consider the SURROUNDINGS….
• System is SO SMALL compared to surroundings
• Surroundings is an “infinitely large reservoir”
• Any heat or work exchanged between system and surroundings can

only alter the properties of the surroundings by an infinitesimal
amount
We can forget about the
path, thus
Remember that infinitesimal changes are characteristic of
reversible processes! qsurr
(dqsurr )rev = (dqsurr )irrev = dqsurr Ssurr =
Tsurr
CHEM 2011
consider again the isothermal expansion of an ideal gas, where we
said that the heat absorbed by the SYSTEM is:
 V2 
qsys = nRT ln 
 V1 
so heat lost by the SURROUNDINGS is: T is constant since isothermal

Tsurr=Tsys=T
Suniv = Ssys + Ssurr  V2 

qsurr = - nRT ln 
qsys qsurr  V1 
= +
T T  V2    V2 
Suniv = nR ln  + − nR ln  = 0
 V1    V1 
For a reversible process
CHEM 2011
Yet since no work is done in the process there is no heat exchange
between system and surroundings
qsurr = 0 and Ssurr = 0
 V2 
For an IRREVERSIBLE EXPANSION Suniv = nR ln  + 0  0
……extreme case...gas is  V1 
expanding into vacuum
 V2  For a REVERSIBLE process Suniv = 0

Ssys = nR ln 
 V1  For an IRREVERSIBLE process Suniv  0
OVERALL Suniv  0
CHEM 2011
“the entropy of an isolated system increases in an irreversible process and remains

unchanged in a reversible process”
ENTROPY CAN NEVER DECREASE
ΔSsurr or ΔSsys can be a negative quantity but their sum must never be less than zero.
For a REVERSIBLE process Suniv = 0

For an IRREVERSIBLE process Suniv  0
OVERALL Suniv  0
CHEM 2011
An ideal gas in thermal contact with the surroundings is cooled
as it expands irreversibly at a constant pressure.
A) ΔS > 0; ΔSsurr > 0; ΔStot > 0
B) Can not determine sign of ΔS; ΔSsurr > 0; ΔStot > 0
C) ΔS > 0; ΔSsurr < 0; ΔStot > 0
D) ΔS < 0; ΔSsurr > 0; Δstot<0

CHEM 2011
EXAMPLE: One mole of an ideal gas at 25°C is allowed to expand adiabatically
and irreversibly from 1L to 10 L with no work done. What is the final
temperature of the gas? Calculate the values of ΔSsys, ΔSsurr and ΔSuniv.
ΔU=q+w=0+0 =0…..temperature does not change for a free expansion (against

vacuum)
 V2 
ΔS must be calculated from a reversible process: Ssys = nR ln 
 V1 
 10 
Ssys = ( 8.3145)ln  = 19.1 J / Kmol
1
Ssurr = 0 since q = 0
Suniv = 19.1 J / Kmol

CHEM 2011
CH 5: ENTROPY & 2nd LAW An entropy change is associated with
phase transitions….
SOLID
S° (J/Kmol)
ENTROPY increases when H2O(s) 45
going from a solid to a
liquid to a gas because H2O(l) 69.9
number of possible states LIQUID H2O(g) 188.7
for molecules increases….
(i.e. degree of molecular
order changes)
GAS
CHEM 2011
Tfus
HEAT OF FUSION (ΔfusH) solid liquid
e.g. ΔfusS° H2O = 22 J/K mol (T = 273.15 K)
Tb
HEAT OF VAPORIZATION (ΔvapH) liquid gas
e.g. ΔvapS° H2O = 109.0 J/K mol (T = 373 K)
• in general ΔvapS° > ΔfusS° for the same substance
• solid to liquid transitions result in a relatively small increase in molecular disorder
• arrangement of molecules in gaseous state is completely random.

liquid to vapour transition….large increase in disorder.
CHEM 2011
 vapH
Svap =
Tb
 H
S fus = fus Smgas  Smliquid  Smsolid
Tf
The molar entropy of O2 is shown as a function of temperature. The

vertical dashed lines indicate constant temperature-phase transitions.
CHEM 2011
Htrans
S FOR PHASE TRANSITIONS Ssys =
Ttrans
Here we are calculating the entropy change for the system.
Heat is absorbed reversibly in an equilibrium process so the changes in entropy

for the surroundings at a phase transition will be given by:
− Htrans
Ssurr =
Ttrans
Therefore, the total change in entropy for the universe will be zero
(at a phase transition).
CHEM 2011
TEMPERATURE DEPENDENCE OF ENTROPY
 T2 
S = nCP ln 
 T1 
S FOR PHASE TRANSITIONS
Htrans
S =
Ttrans
CHEM 2011
EXAMPLE
Calculate ΔS when a sample (of one mole) of H2O(l) is heated

from 25°C to 100°C, and then following vaporization, the
H2O(g) is further heated to 160°C.

S = CP (H2O(l ) )ln
373   433 
 + Hvap / 373 + CP (H2O(g ) )ln 
 298   373 
heating water phase transition heating vapour

CHEM 2011
If you had to calculate the total change in entropy as 5 g of ice
at -20°C are heated to water vapour at 120, how many
different steps (terms) would your calculation need?
A) 2
B) 3
C) 4
D) 5
CHEM 2011
CH 5: ENTROPY & 2nd LAW 𝑺 = 𝒌𝒃 𝒍𝒏𝑾
The entropy of a perfect

crystal at 0 K is zero. CRYSTAL AT T = 0K CRYSTAL AT T > 0K
The third law provides the reference Perfectly oriented Randomly oriented
state for use in calculating absolute For one mole of molecules At T > 0, thermal motion
entropies. contributes to the entropy of the
There is only one microstate at T = 0
substance so that it is no longer
W = 1(6.02 ×10 ) = 1
23
zero
S = k ln(1) = 0 W>1 S>0
lim 𝑆 = 0 lim CP = lim CV = 0

𝑇→0 T →0 T →0
CHEM 2011
CH 5: ENTROPY & 2nd LAW lim CP = lim CV = 0
T →0 T →0
Special physical phenomena can be observed at very low

temperatures, such as superconductivity and superfluidity…
THE QUEST FOR T → 0

IN THE LAB
BOOMERANG NEBULA current world record : cooling a piece of
rhodium metal to 100 picokelvin
• a protoplanetary nebula located 5,000 light-years away from Earth

• The nebula is measured at 1 K (−272.15 °C;), the naturally coldest place known
in the universe.
• The Boomerang Nebula was formed from the outflow of gas from a star at its
core. The gas is moving outwards at a speed of about 164 km/s and expanding
rapidly as it moves out into space. This expansion is the cause of the nebula's very
Credit: NASA/ESA low temperature.
CHEM 2011
Entropy defined experimentally using:
qreversible,p = Cp dT plus contribution from fusion or vaporization
Tfusion Tboil Tfinal

CPsoliddT H fusion CPliqdT Hvaporization CPgasdT
( T ) = S( 0K ) +  + +  + + 
gas
S
0
T Tfusion Tfusion
T Tboil Tboil
T
Entropy values tabulated at 298.15K and 1 bar
What if not at 298.15K:

T
nC p T
S = S298 +  dT = S298.15 + nC p ln
T o o
.15
298.15
T 298.15
only valid if no state changes

CHEM 2011
CH 5: ENTROPY & 2nd LAW We can also keep track of entropy changes in a reaction by subtracting S°
(products) from S° (reactants)
∆𝒓 𝑺𝒐 = Σ ν𝒑 𝑺𝒐 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − Σ ν𝒓 𝑺𝒐 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
v are coefficients from balanced chemical equation
EXAMPLE
Calculate the entropy change for the formation of water vapour at 298 K.
2H2(g) + O2(g) → 2H2O(g)
Hydrogen (g) Oxygen (g) Water (g)

S°(J/K mol) 130.57 205.04 188.72
ΔS ( 25C) = 2S H2O(g) − S O2(g) − 2S H2(g)

= 2( 188.72 )-205.04-2( 130.57 ) = -88.74 J/K
CHEM 2011
CH 5: ENTROPY & 2nd LAW If a spark is applied to a mixture of H2(g) and O2(g), an explosion occurs and
water is formed. The gaseous water is cooled to 100°C. Calculate the entropy
change when 2 mol of gaseous H2O is formed at 100°C and 1 atm from H2(g)
and O2(g) at the same temperature and each at a particular pressure of 1 atm.
2H2(g) + O2(g) → 2H2O(g)
ΔS ( 25C) = 2S H2O(g) − S O2(g) − 2S H2(g)

= 2( 188.72 )-205.04-2( 130.57 ) = -88.74 J/K
To find ΔS at (100°C, 1 atm), we need to know the heat capacities of the reactants
and products (can get them from a constant table)
ΔCP ( 25C) = 2C P H2O(g) − C P O2(g) − 2C P H2(g)
= 2( 33.6 )-29.4-2( 28.8 ) = -19.8 J/K
373 dT
ΔS( 100C) = ΔS( 25C) + 298 CP
T
373
= -88.74 J/K − 19.8 ln = −93.18 J / K
298
CHEM 2011 Consider this reaction and calculate the entropy of the reaction mixture, surroundings and
CH 5: ENTROPY & 2nd LAW the universe at 298 K. Why is your result reassuring to Earth’s inhabitants?
N2 (g) + O2 (g) → 2NO (g) N2 (g) O2 (g) NO (g)
ΔH°f (kJ/mol) 0 0 90.4

S°(J/K mol) 191.6 205.0 210.6
The standard entropy for this reaction is:

ΔSreaction =  νi Sf,i = 2  (210.6 J K-1 mol−1 ) − (191.6 J K-1 mol−1 ) − (205.0 J K-1 mol−1 ) = 24.6 J K-1 mol-1
i
The standard enthalpy for this reaction is:


ΔHreaction =  νi Hf,i = 2  (90.4 kJ mol−1 ) − (0 kJ mol−1 ) − (0 kJ mol−1 ) = 180.8 kJ mol-1
i
And the entropies for the surroundings and universe:
ΔSsurroundin gs =
- dq − Hreaction
=

=
(- 180800 J mol-1 )
= −607 J mol-1 K−1
T T (298.0 K)
ΔSuniverse = ΔSreaction + ΔSsurroundings = (24.7 J K-1 mol-1 ) + (- 607 J K-1 mol-1 ) = −582 J mol-1 K−1
CHEM 2011
CH 5: ENTROPY & 2nd LAW HEAT ENGINE converts heat to mechanical work
E.g. steam locomotives, steam turbines..
Hot reservoir CARNOT ENGINE is an idealized model of a heat engine

REVERSIBLE CARNOT CYCLE
A CYCLIC AND REVERSIBLE PROCESS
qhot • Isothermal expansion
• Adiabatic expansion
• Isothermal compression
• Adiabatic compression
qcold
There is a natural symmetry between converting work to heat
and converting heat to work. Thermodynamics provides an
Cold reservoir explanation for this asymmetry.
CHEM 2011 ▪ Entropy increases cause irreversible changes
CH 5: ENTROPY & 2nd LAW ▪ Some energy lost as waste heat
▪ Amount of work system can do therefore limited
1
P1
2
P2
P4
4
P3 3
V1 V4 V2 V3
http://galileoandeinstein.physics.virginia.edu/more_stuff/flashlets/carnot.htm
CHEM 2011
In how many steps is q>0 in the Carnot cycle
A) 1
B) 2
C) 3
D) 4
CHEM 2011 STEP 1: ISOTHERMAL EXPANSION
INITIAL STATE: P1, V1, T2
FINAL STATE: P2, V2, T2
(isothermal process, ideal gas)
U = 0
(isothermal expansion, ideal gas)

V2
work done = w2 = −RT2 ln
V1
V2
heat absorbed = q2 = RT2 ln (q2 = -w2)
V1
Since V2 > V1 q2 > 0
CHEM 2011 STEP 2: ADIABATIC EXPANSION
(adiabatic process)
q=0
(assume CV to be T.-independent)
work done = U = CV (T1 − T2 )

CHEM 2011 STEP 1: ISOTHERMAL COMPRESSION
(isothermal process, ideal gas)
U = 0
(isothermal expansion, ideal gas)
V4
work done = w1 = −RT1 ln
V3
V4
heat absorbed = q1 = RT1 ln (q1 = -w1)
V3
Since V3 > V4 q1 < 0
CHEM 2011 STEP 4: ADIABATIC COMPRESSION
(adiabatic process)
q=0
(assume CV to be T.-independent)
work done = U = CV ( T2 − T1 )
CHEM 2011
CH 5: ENTROPY & 2nd LAW CYCLIC PROCESS
U (cycle) = 0 (ΔU is a state function)
q(cycle ) = q1 + q2 (q2 is positive and q1 is negative)
V2 V4
w( cycle ) = − RT2 ln + C V ( T1 − T2 ) − RT1 ln + C V ( T2 − T1 )
V1 V3
V V
w( cycle ) = − RT2 ln 2 − RT1 ln 4
V1 V3
CHEM 2011
CH 5: ENTROPY & 2nd LAW CYCLIC PROCESS
Using P-V relations for isothermal and V2 V3

=
adiabatic processes, one can find that: V1 V4
V2 V
w( cycle ) = − RT2 ln − RT1 ln 4
V1 V3
V2
Substituting back in: w(cycle) = − R(T2 − T1 )ln
V1
V2 V4 V2
And: q2 = RT2 ln q1 = RT1 ln = −RT1 ln
V1 V3 V1
CHEM 2011
CH 5: ENTROPY & 2nd LAW EFFICIENCY of the heat engine:
net work done by heat engine
 = efficiency =
heat absorbed by engine
w
=
q2
R(T − T )ln(V2 / V1 )
= 2 1
RT2 ln(V2 / V1 )
T −T T
= 2 1 =1- 1
T2 T2
The efficiency of this reversible heat engine can approach one only as
T2 ∞ or T1  0, neither of which can be accomplished in practice. Therefore, heat can never be totally
converted to work in a reversible cycle process.
Also, since wcycle (irrev) < wcycle (rev) εirrev < εrev < 1
CHEM 2011
CH 5: ENTROPY & 2nd LAW Q In a wood burning power plant the steam in the turbine operates
between the high temperature of 810 K and a low temperature of
366 K. What is the Carnot efficiency for this plant?
T1 366
 =1-  = 1- = 0.55
T2 810
Compare this to the efficiency calculated form electrical power

output of 59 MW and heat power input of 165 MW.
W P 59 MW
= = = = 0.35
Q H 165 MW
The actual efficiency is less than the Carnot efficiency!

CHEM 2011
Combining different expressions for efficiency:
q1 + q2 T2 − T1
= = q2 + q1 is the reversible heat qreversible/T for the Carnot cycle
q2 T2
Change in a cyclic loop is zero therefore a state function
q1 T1
1+ −1+ = 0
q2 T2
q2 q1
+ =0 dqreversible
T2 T1 S =  = ENTROPY
T
dqreversible
 T =0
CRITICAL: ΔS must be calculated along a reversible path
CHEM 2011 STEP 1: (15, 75) to (15, 150)
CH 5: ENTROPY & 2nd LAW w=0 (const V)
q= ΔU=CV (T2-T1) =3/2 R(P2V2/R - P1V1/R)
q= ΔU=3/2(15 × 150 – 15 × 75) = 1690 J
STEP 2: (15, 150) to (35, 150)

w=-PΔV = -150(35 – 15 ) = -3000 J
q= CP (T3-T2) =5/2 R(P3V3/R - P2V2/R)
q= 5/2(35 × 150 – 15 × 150) = 7500 J
ΔU=q+w = 4500 J
STEP 3: (35, 150) to (15, 75)

w= area under the curve= 3/2(75 × 20) = 2250 J
q= ΔU -w= -8440 J
ΔU= 0- (1690 + 4500) = - 6190 J (cyclic process)
wcyc = -750 J w 750

qcyc = 750 J = = = 8.2%
ΔUcyc= 0 J
qpositive 1690 + 7500

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CHEM 2011

CH 5: ENTROPY & 2nd LAW

*typo in a), but right final answer

The greater the degree of

Easy to predict in the physical world:

Water flows and balls roll downhill

Sugar cube above Sugar cube dissolved

A catalyst can increase the rate of a

A catalyst cannot do so for a non-

Non-spontaneous processes are not

Some spontaneous processes can be very slow

Free expansion of gas

Free compression of gas

HIGH TEMP LOW TEMP Increase in entropy

Potential energy represents nondispered energy, thermal

• Floor becomes warmer

• Eventually ball comes to rest: all of its KE transferred to the floor.

Inelastic Collisions Conversion of PE and KE into internal energy

• For this process to occur, the

Why doesn’t the coffee

FIRST LAW OF THERMODYNAMICS

focus on large-scale properties of matter focus on the concept of molecules

Position, velocity, mass, describing the

kb Boltzmann constant = 1.38 × 10−23 J/K

The macrostate is the

A microstate is a single possible

A hot and a cold bar, each made up of 4

If there are N atoms and

kb= 1.38 × 10−23 J/K

∆𝑺𝒔𝒚𝒔 = 𝒌𝒃 𝒍𝒏𝟐𝟎 − 𝒌𝒃 𝒍𝒏𝟒 = 𝟐. 𝟐𝟐 × 𝟏𝟎−𝟐𝟑 𝑱/𝑲

𝜟𝑺𝒔𝒖𝒓𝒓 = 𝒌𝒃 𝒍𝒏𝟐𝟎 − 𝒌𝒃 𝒍𝒏𝟓𝟔 = −𝟏. 𝟒𝟐 × 𝟏𝟎−𝟐𝟑 𝑱/𝑲

𝜟𝑺𝒖𝒏𝒊𝒗𝒆𝒓𝒔𝒆 = −𝟏. 𝟑𝟓 × 𝟏𝟎−𝟐𝟑 𝑱/𝑲

Allowed energy levels for a He

Probabilities for a He atom of

• The probability of finding an He atom in ½ the volume (i.e. V1) = ½

• The probability of finding two He atoms in V1 is (½)(½) or ¼

the probability = W = ( ½ )N where N is no. of atoms

INITIAL STATE (LEAST PROBABLE): all atoms compressed in V1

…spontaneous change occurs from state of low probability of occurring

S = kBW kB = Boltzmann constant = 1.381  10-23J/K

but this equation is actually INCORRECT….

BOLTZMANN EQ. as W increases to W2…S increases to 2S

INITIAL STATE FINAL STATE

ENTROPY is a state function, so it is path independent.

PROBABILITY OF EACH STATE: W1 = (CV1 )N W2 = (CV2 )N

INITIAL STATE FINAL STATE  V2 

V1 (28 g mol-1 ) (V1 )

𝜕𝐶𝑉 𝑇 𝜕(𝑛𝑅 𝑇Τ𝑉 ) q is not a state function , and so

𝒅𝒒𝒓𝒆𝒗 𝑑𝑞𝑟𝑒𝑣 𝐶𝑉 𝑇 𝑛𝑅 Dividing both sides by T gives an

Change in T at constant V: qreversible = nCvdT

Change in T at constant P: qreversible = nCPdT

C) It depends on the magnitude of the change in

Add component under isothermal conditions due to P or V change and then

Entropy in different situations we have thought about

Reversible adiabatic process 0  0

Reversible isothermal expansion or compression -wreversible = n R T ln Vf/Vi n R ln Vf/Vi

Reversible/irreversible change in T at constant V nCvdT nCvlnTf/Ti

Reversible/irreversible change in T at constant P nCpdT nCplnTf/Ti

Consider entropy change for following processes: ΔS

Increasing volume of a gas n R ln Vf/Vi +

ΔSsystem + ΔSsurroundings >0

(1) CaCO3(s) CaO(s) + CO2(g) 

(2) 2H2(g) + O2(g) 2H2O(l) 

(3) N2(g) + O2(g) 2NO(g) 