The Basic Concepts: the system

Thermodynamics System Matter System

The First Law Energy Matter
Work, Heat, Energy Energy
Surroundings Surroundings
(a) open (b) closed
Thermodynamics is the study of
System
the transformations of energy. Matter

Energy
Oxtoby, Chapter 10 (10.1-10.4) (c) isolated
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The Basic Concepts: state and path fns The Conservation of Energy:
A state function, X, is a property that depends only on the current state
of the system, and not on how it was prepared.
Changes in a state function depend only on the start and end
Energy can neither be created not destroyed
points of an experiment (experimental observation)
DX = Xfinal – Xinitial
e.g. the duration of this lecture depends only when I start and fl Energy is a state function
when I finish
A path function, Y, is a property that depends on the history of the
system. The principle of conservation of energy can be used to assess
e.g. the boredom/interest factor for this lecture depends on a lot the energy changes that accompany physical and chemical
more than just my first and last sentence processes.

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Work, Heat and Energy

ICE + heat Liquid water
Melting
SOLID + heat Liquid Work, w, is done when an object is moved against an opposing force

C + O2 CO2 + heat

Work is a path function Expanding gas pushes out piston

(how strong is gravity?) against (e.g, atmospheric) pressure
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 Work, Heat and Energy Heat, q

When the energy of a system changes as a result of a temperature

The Energy, E of a system is its capacity to do work.
difference between it and its surroundings, it is said that energy has
When spring unwinds, been transferred as Heat, q
work will be done
Processes that release energy as heat are exothermic;
Increasing its capacity to work
A B + heat
Combustion reactions

When piston moves out
against higher pressure,
work will be done
Processes that absorb energy as heat are endothermic;
A + heat B
Melting, Vaporization of Water

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The First Law Hence, for an isolated system:

In thermodynamics, the “total” energy of a system is called the ∆Euniverse = 0
internal energy, E. System
Matter ∆E = w + q = 0 + 0 = 0
Experiments measure the change in energy between start and finish:
Energy
∆E = Ef - Ei
Surroundings
The change in internal energy ∆E is the sum of work done on a and a closed system:
system and the energy transferred as heat to a system according to;
∆E = w + q System the change in internal energy of
Heat must be a path function: the system can gain/lose energy either Matter a closed system is equal to the
as heat or as work. energy that passed through its
Energy
boundary — either as heat or as
SI unit for work, heat and energy is the Joule (or J/mol, kJ/mol, …)
Surroundings work.
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Work, w Work and pressure

In general: w=F. d Pressure -
External pressure, p
work distance Volume Work:
Force along path
Area A
∆h
More specifically, for thermodynamics:
w = - Fext . d
w=- F. d w = - Fext ∆ h
We focus on the force the system has to push against w = - pext A ∆ h
Work is done on system by the surroundings w = - pext ∆ V
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 Work, and pressure +/-? The Sign Convention
w = - pext ∆ V
For pext = 0
Work done by the system on its surroundings is “lost” by the
system (a negative w).
Expansion ∆ V > 0 Compression ∆ V < 0 Work done on the system by the surrounding increases the
internal energy (positive w) – energy is stored in the system

A positive heat flow (positive q) corresponds to heat gained

by the system.
Hence, a heat loss is to be understood as a negative gain
w < 0, hence system w > 0, hence (negative q).
performs work on surroundings perform
work on system Thermal Equilibrium is established when two bodies have
surroundings
the same temperature.
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Example: Recall:
Calculate the work done when 25g of iron reacts with Hydrochloric Acid ∆E = w + q
in (a) a closed cell, (b) in a open beaker at 25oC?
& w = - pext ∆V
(a) ∆ V = 0 w=0
If the system is kept at constant volume:
(b) Fes + 2 HCl(aq) FeCl2 (aq) + H2(g) ∆E = qv
w = - pext ∆ V ∆ V = Vf-Vi =Vgas pV = nRT n= m/M We measure ∆E usually using Calorimetry (the measurement
25g mol of amounts of heat flowing into or out of a system and the
w = - pext ∆ V = - pext Vgas = - n R T 55.845 g accompanying temperature changes)
= 0.45 mol
- 0.45mol x 8.314 J x 298 K
w= = - 1.2 kJ
K mol
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Calorimetry Examples
Adiabatic Bomb Calorimeter Adiabatic means no heat is transferred (a) When 100 g of Napthalene was burned in a bomb calorimeter
from calorimeter to surroundings releasing heat of 3.91 kJ, the temperature rose by 3.01 K. What is the
calorimeter constant?
The change in temperature, ∆T, of the
calorimeter is proportional to the heat q = Ccal ∆T 3.91 kJ = Ccal µ 3.01 K
that the reaction releases or absorbs. Ccal = 1.30 kJ / K
q = Ccal ∆T
(b) 10.0 A from a 12 V battery were passed through the heater of a
Calorimeter Constant calorimeter for 150 s. The temperature rose by 5 K. What is the
Calibrated using a process of known energy output calorimeter constant?
(eg, burning of a substance of known mass) or
from an electrical current, I, of known potential, V
q = (10.0 A) µ (12 V) µ (150 s)=1.8 µ 104 A V s = 18 kJ
q=VIt 18 kJ = Ccal µ 5 K Ccal = 3.6 kJ / K
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 Heat Capacity Heat Capacity
q
Generally: C = Units: J K-1, cal K-1 1 cal = 4.184 J
∆T
Molar Heat Capacity (J K-1 mol-1 or cal K-1 mol-1)
q C Heat capacity of a sample divided by the
c= =
∆T n n chemical amount of substance, n

The heat capacity C of a substance is the heat required to change its

Specific Heat Capacity (in J K-1 kg-1 or cal K-1 kg-1)
temperature by one Kelvin, and has units of energy per Kelvin. q C Heat capacity of a sample divided by the
cs = ∆T m = m mass of substance, m
The heat capacity is an extensive variable: the quantity is proportional to
the amount of matter present. c = M cs
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Heat Capacity Example:

measured at constant pressure measured at constant volume A new calorimeter is filled with 200g of room temperature
(eg, conduct experiments in water. Adding 1212 J of heat to the contents, raises the
closed container) interior temperature by 1.42 K. Calculate the calorimeter
constant given that the molar heat capacity of water, cp(H2O)
qp qv is 75.38 J K-1 mol-1.
Cp = ∆T Cv = ∆T
1212 J = qwater+ qcalorimeter = Ccal ∆T + cp(H2O) n(H2O) ∆T
qp Cp qv Cv
cp = = molar cv = = = Ccal ∆T + cp(H2O) m(H2O) ∆T
∆T n n ∆T n n M(H2O)
1212 J - 75.38 J K-1 mol-1 200 g 1.42 K
If reaction contains only solids and/or liquids, cp ≈ cv Ccal = = 16 J K-1
1.42 K 1.42 K 18 g mol-1
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Recall: ∆E = w + q
& w = - pext ∆V
If the system is kept at constant volume:

Enthalpy ∆E = qv
But if it is not kept at constant volume?

∆E = qv
Another type of energy, the ENTHALPY, is useful in these
circumstances
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 The Enthalpy, H Example: Relating ∆H and ∆U
The internal energy change when 0.500 mol calcite (ρc =2.71 g cm-3)
converts to aragonite (ρa =2.93 gcm-3) is 0.100 kJ. Calculate the
For a system kept at constant pressure:
difference between the changes in enthalpy and in internal energy at a
∆H = qp where ∆H = Hf - Hi pressure of 1 atm. [calcite and aragonite are different forms of CaCO3]
H = U + pV
∆H = ∆(U+pV)=Hf - Hi = (U+pV)a - (U+pV)c
The Enthalpy, like the internal Energy, is a state function = Ua - Uc + (pV)a -(pV)c
= ∆ U + p ∆V as p = const.
m
The Enthalpy is related to the Energy by: ∆H- ∆U = p ∆V Va = ρ a
a
H = U + pV = U + nRT Ma = Mc = 100 g/mol Va = 17.0 cm3
for an ideal gas ∆H- ∆U = 0.152 J ma = mc = 50.0 g Vc = 18.5 cm3
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Enthalpy of Reaction - ∆Hr The Reaction Enthalpy, ∆Hr

Example 1) A B In General: ∆Hr = Hproducts - Hreactants
HA HB
∆Hr = Σ ν Hproducts - Σ ν Hreactants
Enthalpy of Reaction: ∆Hr = HB - HA
Sum over all standard molar enthalpies taking
into account their stochiometric factors, ν
Example:
Example 2) 2C + D E +3F
2 C2H6 + 7 O2 4 CO2 + 6 H2O
2 HC HD HE 3 HF
ν= 2 ν= 7 ν= 4 ν= 6
Enthalpy of Reaction: ∆Hr = HE + 3 HF - HD - 2 HC
∆Hr = 6H(H2O) + 4H(CO2) - 7H(O2) - 2H(C2H6)
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Standard Enthalpies Enthalpies of phase change

Enthalpy are normally tabulated for substances in their standard state; Enthalpy changes also occur when a substance melts/freezes or
these are called the standard enthalpy, Ho. Denotes standard condition
condenses/evaporates
The standard state of a substance at a specified temperature is its pure
form at 1 atm (should now be 1 bar). Fusion (melting): H2O(s) kJ
H2O(l) ∆Hofus(273)=+6.0 mol
For dissolved species, the standard state is the concentration of 1M Vaporisation (boiling): H O kJ
under a pressure of 1 atm at a specified temperature. 2 (l) H2O(g) ∆Hovap(373)=+40.7 mol

Standard enthalpies at T = 298 K are often denoted Hʅ

endothermic!
Hence, the standard enthalpy of reaction is kJ
Sublimation H2O(s) H2O(g) ∆Hosub(298.15)=+46.7 mol
∆Hro =Σν Ho products - Σν Ho reactants (direct conversion from solid to gas)

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Rules for enthalpy changes (1) Rules for enthalpy changes (2)
Enthalpy is a state function fl can derive some rules A change in enthalpy is independent of the path taken
between two states:
∆Hovap(373 K)= + 40.7 kJ mol–1 Initial state Final state
vaporisation Sublimation H2O(s) H2O(g)
(1) H2O(l) H2O(g)
condensation ∆Hosub
solid gas
∆Hocond(373 K)= - 40.7 kJ mol–1 ∆Hofus ∆Hovap
solid gas
In general: ∆Ho(A→B) = - ∆Ho(B→A)
the enthalpy of a forward process differs from that of the backwards ∆Hosub = ∆Hofus + ∆Hovap
process only in sign.
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One could also have written … Hess’s Law

The enthalpy of an overall reaction is the sum of the
H2O(s) H2O(l) ∆Hofus = +6.0 kJ mol–1 enthalpies of the individual reactions into which the
reaction can be divided.
H2O(l) H2O(g) ∆Hovap = +40.7 kJ mol–1

Overall: H2O(s) H2O(g) ∆Hosub = +6.0 + 40.7 kJ mol–1

Example: Calculate the enthalpy of combustion of benzene (C6H6)
= + 46.7 kJ mol–1 from its enthalpy of hydrogenation (-205 kJ/mol) to
cyclohexane, and the enthalpy of combustion of
cyclohexane (∆Ho (C6H12) = –3920 kJ/mol)). The enthalpy
Because enthalpy is a state function, these rules apply to every type of of the combustion for H2 is -286 kJ/mol.
reaction or change

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Enthalpy of Combustion of Benzene Standard Molar Enthalpies of Formation, ∆Hof

We want to know: C6H6 + 7.5 O2 6 CO2 + 3 H2 O The enthalpy of formation is the enthalpy change when a compound is
formed from its elements, and those elements are in their most stable
We do know:
form under the prevailing conditions.
C6 H6 + 3 H2 C6H12 -205 kJ/mol
C6H12 + 9 O2 6 CO2 + 6 H2O -3920 kJ/mol When the prevailing conditions are the standard state, this is called the
standard enthalpy of formation, ∆Hof
3 H2 O 3H2 + 1.5 O2 -(3 µ -286) kJ/mol
H2(g) + 0.5 O2(g) H2O(l) ∆Hof = - 286 kJ/mol

C6 H6 + 7.5 O2 6 CO2 + 3 H2O -3268 kJ/mol 6 C(s, graphite) + 3 H2(g) C6 H6(l) ∆Hof = + 49 kJ/mol

The standard enthalpies of elements in their reference states are zero

at all temperatures (graphite is the reference state of carbon!).

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Bond enthalpies Applications of bond enthalpies
Using average bond enthalpies, estimate the enthalpy change for
A–B(g) A(g) + B(g) ∆Hrxn = energy of the A–B bond
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(g)
But bond enthalpies are affected by the neighbouring bonds
CH4(g) CH3(g) + H(g) ∆H = 439 kJ mol–1 Step 1: what bonds are in the reactants (draw Lewis structures)
C2H6(g) C2H5(g) + H(g) ∆H = 410 kJ mol–1
C3H8(g) H H H
CHCl3 (g) CCl3(g ) + H(g) ∆H = 380 kJ mol–1
H C C C H
O2
fl usually tabulate average bond enthalpies (determined from A–B H H H O O
bond enthalpies in many different A–B containing molecules)
1 µ (8 C-H bonds),
5 µ (1 O=O double bond)
1 µ (2 C-C bonds)
Average bond enthalpies can be used to estimate the enthalpy of a
compound: just count the number and type of bonds involved. nb: angles are not 90o
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Step 2: what bonds are in the products (draw Lewis structures)

Finally…
3 CO2 4 H2O DHrxn º 8 µ 412 + 2 µ 348 + 5 µ 497
O – 6 µ 743 – 8 µ 463) kJ mol–1
O C O H H = –1685 kJ mol–1
3 µ (2 µ CO double bonds) 4 µ (2 µ OH single bonds) Value from calorimetry experiments:
∆Hco = -2220 kJ/mol

Step 3: calculate the net breakage / formation of bonds: energy is Bond enthalpies appear to give a 30% error!
absorbed in breaking reactant bonds, and released it in making them • Works better when not all bonds are being broken (1st, 2nd, 3rd and
DHrxn º 8H(C–H) + 2H(C–C) + 5H(O=O) 4th C–H bonds in methane have very different strengths)
– 6H(C=O) – 8H(O–H)
• better to use thermochemical groups bonded to at least two other
atoms rather than individual bonds
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Spontaneous Changes:
Why do some processes happen spontaneously?
•Why does a hot body get cooler (rather than hotter) when
surrounded by a cooler medium?

Entropy •Why does a gas expand into all available volume of a container
rather than contract?

The driving force for spontaneous change (change that happens

without intervention — doing work or heating) is described in the
second law of Thermodynamics

Chapter 11
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No process is possible in which the sole result is the absorption of heat Entropy, S, and the second law
from a reservoir and its complete conversion into work.
These spontaneous changes happen because they increase the
randomness with which energy is spread through an isolated system
Kinetic energy converted Energy is not accumulated in ball
into thermal motion and thermal motion is not directional
The Entropy, S, a thermodynamic state function, is a measure of
“molecular disorder”, or “freedom of movement” molecules have, and
helps us to define the direction of spontaneous change

The Entropy of an isolated system increases in the course of a

spontaneous change

∆Ssystem + ∆Ssurroundings = ∆Stotal > 0

Hence, in a spontaneous process: ∆Suniverse > 0

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Entropy and Equilibrium Entropy and Heat

Nothing changes when a system is at equilibrium, including the Entropy measures dispersal of energy in a system
entropy of the system Heat changes kinetic energy of molecules, i.e. disperses energy by
So, for any process increasing the velocities of all the molecules
∆Ssystem + ∆Ssurroundings = ∆Suniverse r 0 fl heat and entropy are related?
But, equilibrium is dynamic at a microscopic level
reactants Ý products For a reversible process

This introduces the idea that changes can be reversible, i.e. a change DS = qrev / T = DH / T (at constant pressure)
can be made, and then exactly undone (“reversed”), so For an irreversible process
∆Suniverse = 0 for a reversible process DS > qrev / T

In practice, reversible changes are an idealised limit in which changes happen

infinitely slowly via a series of imperceptible shifts in the equilibrium
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Entropy and Disorder But …

The Entropy of the System Water freezes (spontaneously) on a cold night!

Entropy
increases ??

Solid Liquid Gas

Entropy of system increases
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Solid (molecules fixed in
Liquid (water molecules
crystal)
able to move)
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Spontaneous Freezing Entropy of Phase Changes

Water freezing is an exothermic process System at transition temperature

H2O(l) H2O(s) ∆H = - 6.88 kJ/mol

So heat is put into the surroundings

–∆ Hsystem = + ∆ Hsurroundings= qp,surroundings b ∆ Ssurroundings

Solid
∆Hfus Liquid
decreases increases ∆SSysfus =
TFus
∆Ssystem + ∆Ssurroundings = ∆Suniverse > 0 ∆Hvap
similarly, for vaporization ∆SSysvap =
Entropy is not the final determinant of spontaneity — see tomorrow Tvap
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Entropy of Reaction Trends in entropy

As entropy is a state function, the entropy of reaction is defined (by Increasing Temperature
analogy to Hess’ law for the enthalpy) as the difference between the
molar entropies for the pure, separated products and the pure,
separated reactants:

∆Sr = Σ ν Soproducts - Σ ν Soreactants

Where o as before indicates that all substances are in their standard

translation rotation vibration
states at the specified temperature.
More modes to distribute energy become available
ENTROPY INCREASES
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Entropy and Disorder: the microscopic view The Statistical Entropy

Let’s say you are tossing a coin with your mates to check who will
have to go to the next lecture to take notes (if handouts are not
Increase in provided). You decide on head and your mate on tails. As you toss the
coin for the first time, the likelihood that of head:tail is 50:50, or
Entropy 1/2:1/2.
Tail Head
# of combinations 1 1

Example: mixing of two gases (pure O2 and pure N2) The chance that you win heads twice is ¼, as it is to win tails twice;
the mixed result has a probability of ½
To quantify S, see microstate considerations below
Tail/Tail Tail/Head or Head/Tail Head
# 1 2 1
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 For three throw Similarly for particles in boxes
T/T/T TTH,THT,HHT HHT,HHT,THH H/H/H Imagine you have four balls and can put them into two containers (T or
H) then you can distribute them as follows;
# 1 3 3 1

Most likely outcome TTTH,TTHT, TTHH,THHT,HTTH, HHHT,HHTH,

T/T/T/T THTT, HTTT THTH, HTHT,HTTH HTHH, THHH H/H/H/H
…. and for four throws
# 1 4 6 4 1
TTTH,TTHT, TTHH, THHT, THTH, HHHT,HHTH,
T/T/T/T THTT, HTTT HHTT, HTHT, HTTH HTHH, THHH H/H/H/H

# 1 4 6 4 1
T H T H T H T H T H
Even split most favored
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The Boltzmann Formula Third Law of Thermodynamics

The entropy change for any equilibrium between pure substance
becomes zero as the temperature approaches absolute zero

S = k ln W The Entropy of any crystalline substance approaches zero as

T | 0 K.

Walther Nernst 1864-1941

W = weight of most probable configuration of the system! Nobel Laureate in chemistry in recognition of his
work in thermochemistry
k = Boltzmann constant = R/N0 = 1.308630 x 10-23 J K-1

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The third law Let’s remember when processes are

S = k ln W
spontaneous
As T | 0 K, every atoms is located at the perfect crystal
location, so W = 1 ∆Suni > 0 Spontaneous
But …
•Removing every defect is difficult (if not impossible) ∆Suni = 0 Equilibrium; also true for idealised
•QM ensures atoms still have zero-point energy, and so some
changes that are so slow they never
entropy persists (see last week) disturb equilibrium (reversible)
fl can’t actually achieve absolute zero ∆Suni < 0 Does not happen (reverse reaction
Temperatures < 0.000001 K have been achieved will be spontaneous)

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 The Gibbs Free Energy, G
∆Suni = ∆Ssystem + ∆Ssurroundings

Requires knowledge of both system and surroundings

Gibbs Free Energy, G At constant pressure and temperature, and for reversible changes:
T∆Ssurroundings = qp,rev = –∆Hsystem

Define a new form of the energy function

G = H – TS
Called the Gibbs free energy.

G is a state function

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The Gibbs Free Energy: criterion for spontaneity Criterion for Spontaneity

At constant T: ∆Gsys = ∆ (Hsys - Tsys Ssys) = ∆Hsys - T ∆Ssys

∆Suni > 0 Spontaneous ∆Gsys < 0

∆G = ∆H - T ∆S ∆Suni = 0 Equilibrium ∆Gsys = 0

Not spontaneous
But also: ∆Hsys ∆Suni < 0 (reverse reaction is
∆Gsys > 0
= - ∆Ssurr
T spontaneous)
Resulting in: ∆Gsys = - T ∆Ssurr - T ∆Ssys N.B. left hand describes the whole universe, but right hand is just the
system. We can drive the system in the wrong direction (hence can
= - T (∆Ssurr + ∆Ssys) have reactions where DG is positive, but cannot force the universe to
and as ∆Suni > 0 = - T (∆Suni) < 0 for spontaneous pr. show negative entropy
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Examples ∆G = ∆H - T ∆S
∆G < 0 for spontaneous
Remember ∆Gsys < 0 for spontaneous processes

∆G = ∆H - T ∆S 2) An endothermic process where entropy decreases

1) An exothermic process which also increase entropy

∆H = + ve (>0)
∆G = +ve (>0)
∆H = - ve (<0) ∆S = - ve ; -T ∆S = + ve (>0)
∆G = -ve (<0) NOT spontaneous
∆S = + ve ; -T ∆S = - ve (<0) (reverse reaction would be
spontaneous spontaneous as G is a state
function)

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 ∆G = ∆H - T ∆S ∆G = ∆H - T ∆S
∆G < 0 for spontaneous ∆G < 0 for spontaneous
3) An exothermic process in which entropy decreases (freeze water) 4) An endothermic process in which entropy increases (melting ice)
Depends on relative Depends on relative
∆H = - ve (<0) magnitudes of ∆H and -T ∆H = + ve (>0) magnitudes of ∆H and -T
∆S ∆S
∆S = - ve ; -T ∆S = + ve (>0) ∆S = + ve ; -T ∆S = - ve (<0)

|∆H| < |T ∆S| |∆H| = |T ∆S| |∆H| > |T ∆S| |∆H| < |T ∆S| |∆H| = |T ∆S| |∆H| > |T ∆S|

∆G > 0 ∆G = 0 ∆G < 0 ∆G < 0 ∆G = 0 ∆G > 0

Not spontaneous Equilibrium Spontaneous Spontaneous Equilibrium Not spontaneous

For fixed ∆H and ∆S , spontaneity depends on T For fixed ∆H and ∆S , depends on T

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Driving forces in chemistry Gibbs Energy for Phase Transitions

Two driving forces underpin Chemistry: P = 1atm
¾ Systems tend to a state of minimum enthalpy H2O(s) H2O(l) kJ
∆Hofus(273.15)= + 6.0 mol

¾ Systems tend to a state of maximum entropy H2O(l) H2O(s) kJ

∆Hofrze(273.15)= – 6.0 mol
The Gibbs free energy expresses the balance between these two
∆Hfrze, 273.15
driving forces ∆G = ∆H - T ∆S ∆Sfrze, 273.15
= Tfrze=273.15
DG = DH – T DS (b 0 ?)
∆G273.15 = ∆H273.15 - Tfrze=273.15
Equilibrium ∆S273.15 = 0

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Gibbs Energy for Chemical Reaction

If ∆H and ∆S are independent of temperature (a good, but not perfect,
approximation), then:
As the Gibbs energy is a state function, the (standard) Gibbs energy
T < Tfrze ∆G = ∆H - T ∆S of reaction is defined (in analogy to Hess’ law for the enthalpy) as:

∆G < 0 Spontaneous Freezing ∆Gro = Σ ν Goproducts - Σ ν Goreactants

T > Tfrze ∆G = ∆H - T ∆S Where o as before indicates that all substances are in their standard
states at the specified temperature.
∆G > 0 Spontaneous Melting of Ice
∆Gro = ∆ Hro - T ∆ Sro
Clearly, the spontaneity of freezing (negative ∆S and negative ∆H)
depends on a balance of the entropy and enthalpy

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 Standard Molar Gibbs Energy of Formation Example:

By analogy with the definition of the standard molar Enthalpy of Pt (NH3)2I2, cis Pt (NH3)2I2, trans
formation we define

∆Gfo = ∆ Hfo - T ∆ Sfo

as the standard molar Gibbs energy of formation when 1 mole of a

∆Hfo(298.15K) ∆Gfo (298.15K)
substance forms in a standard state at a specified temperature from the
most stable forms of its constituent elements in standard states at the cis -286.6 kJ/mol -130.2 kJ/mol
same temperature. trans -316.9 kJ/mol -161.5 kJ/mol

Calculate the standard entropy, So, of both compounds at 298.15 K.

Stanford Chemistry Stanford Chemistry

Summer Session 2005 Chem 31 Summer Session 2005 Chem 31

∆ Sfo = ∆ Hfo - ∆ Gfo Gibbs Free Energy & Equilibrium Constants

T
Pt(s) + 2 NH3,(g) + I2,(s) Pt(NH3)2I2 (s)
aAg + bBg cCg + dDg
cis trans
For the “standard” reaction all reactants and products in standard
∆ Sfo = -286.6 + 130.2 kJ/mol ∆ Sfo = (-316.9+161.5) kJ/mol states, but in general they are related by the reaction quotient.
298.15K 298.15K
= -0.5246 kJ/(K mol) = -0.5212 kJ/(K mol) ∆Gr = ∆Gro + RT lnQ

∆ Sfo = So(Pt(NH3)2I2) - So(Pt(s)) - 2 So(NH3,(g)) - So(I2,(s)) N.B. both ∆G and Q can be used to (PC)c (PD)d
determine the direction of change: Q= (PA)a (PB)b
-0.5425 kJ/(K mol)
∆G | 0
So(Pt(NH3)2I2)cis = 17.9 J/(K mol) So(Pt(NH3)2I2)trans = 21.3 J/(K mol) Q | K
Stanford Chemistry Stanford Chemistry
Summer Session 2005 Chem 31 Summer Session 2005 Chem 31

Temperature and the Equilibrium Constant

∆Gr = ∆Gro + RT lnQ
Now remember, at
equilibrium, ∆Gr = 0 ∆Gro = - RT lnK Assume ∆S and ∆ Hro don’t change with temperature!
and Q = K RT1 ln K1 = ∆H − T1∆S
∆Gr = - RT lnK + RT lnQ
= RT ln Q/K RT2 ln K 2 = ∆H − T2 ∆S
G
⎛K ⎞ ∆H − T1∆S ∆H − T2 ∆S
Equilibrium ln ⎜ 1 ⎟ = ln K1 − ln K 2 = −
∆G=0 Q=K ⎝ K2 ⎠ RT1 RT2
Spontaneous 1852-1911
Nobel Prize in
to products The van’t Hoff Equation Chemistry, 1901

∆G<0
Q<K Not spontaneous to K2 ∆Hro
∆G>0
Q>K
reactants ln
K1 = R ( 1T 1
1
T2 )
reactants products
Stanford Chemistry Stanford Chemistry
Summer Session 2005 Chem 31 Summer Session 2005 Chem 31

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Similarly, for liquid-vapour equilibrium
The Clausius-Clapeyron Equation
Example:
Water boils at 373.15K at an atmospheric pressure of 1.0 atm.
Calculate the boiling temperature of water on top of Mt Everest
(assuming a pressure of about 0.36 atm). The enthalpy of
vaporization of water can be assumed to be 40.7 kJ/mol.

P2 ∆Hvapo 1 1
ln = (T ) ∆Hvapo 1
P1 R 1 T2 ln P2 = ( T1 1
)
P1 =1.0 atm P2 = 0.36atm
P1 R T2 T1 = 373.15 K
assuming ∆S & ∆ Hro independent of temperature
∆Hvapo = 40.7 kJ/mol
This expression is particularly useful when you want to determine the 0.36 atm
8.314 J ln 1
boiling points of substances at different pressures. 1 atm 1 1
= =
K mol 40.7 103 J mol-1 373.15 K T2 346 K
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