CHEM*1050 Thermodynamics Notes Summary

Jan 12, 2016
CHEM*1050 – General Chemistry II
Calculus
Atoms
Molecules Statistical
CHEM*1050 Bonding & Structures Methods Bulk Properties
Material Spectroscopy Solution Equilibria
Differential Equations
Quantum mechanics Thermodynamics
Electrochemistry CHEM*1050
Kinetics Material
Differential Equations
Matrix Algebra
Introduction to THERMODYNAMICS NOTES:

• science of the interconversion of different forms of ENERGY
e.g., heat, mechanical work, electrical work, chemical energy, etc.
• an essential foundation for understanding physical and biological sciences.
• at the centre of any physical description of living matter.
Key Questions:
1. Interconversion of energy – how, why, etc. Spontaneous - reaction
2. Is a particular reaction possible? that occurs in a given
3. How much useful work can be obtained from a reaction? set of conditions
4. Can we understand chemical equilibria? without intervention
Chemical reactions involve a transfer of energy between Thermochemistry:

the SYSTEM and SURROUNDINGS study of heat given off
or absorbed in a
DEFINITIONS: chemical reaction
SYSTEM – the part of the universe under observation
e.g., engine, electrical cell, reaction in a flask, etc.
The system can be:
• “Open” – both mass and energy may leave and enter.
e.g., beaker
• “Closed” – energy can be exchanged but no mass can enter or leave.
e.g., sealed flask
• “Isolated” – neither mass nor energy may enter or leave.

e.g., insulated, closed container
SURROUNDINGS – the rest of the universe.

Therefore, the “UNIVERSE” is made up of the “SYSTEM” and the “SURROUNDINGS.
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The “STATE” of a system is characterised by a set of variables, e.g., P, V, T, n, etc. NOTES:
These are STATE VARIABLES. P, V, T, n and mass can be classified as either:
Intensive – independent of size. Extensive – dependent of size.
e.g., P, T, etc. e.g., mass, V, n, etc.
ENERGY TRANSFER
• We can transfer energy in and out of a system, where the INTERNAL
ENERGY of the system may change.
• Internal Energy (U) is the sum of the kinetic and potential energy of system.
Note: In these notes, U will be used to represent the internal energy (as is used
in Ebbing & Gammon). Depending on what text you refer to, E or U are
commonly used to symbolize the internal energy of a system.
• Two ways U can change:

1. Heat (q)
2. Work (w)
Note: Another way is by adding or removing mass but this is not encountered
in a “closed” system.
Gives off heat: Exothermic

ENERGY TRANSFER Takes in heat: Endothermic
HEAT (q) Thermal

SYSTEM
Surroundings
WORK (w)
INTERNAL
ENERGY (U)
Mechanical
Surroundings
We can ONLY measure changes in U, not absolute values,

so for any reaction or process, i.e., Ufinal – Uinitial = ∆U
2
We can only measure changes in U, i.e., U(final) - U(initial) = ∆U
∆U(rxn) = U(products) - U(reactants)
We can change the internal energy, U, by any combination of q and w. NOTES:
∴ ∆U = q + w
This is a statement from the conservation of energy:
1st LAW OF THERMODYNAMICS
The Law of Conservation of Energy states energy may be converted from
one form to another but the total quantity of energy remains constant.
HEAT ENERGY, HEAT TRANSFER and TEMPERATURE

∆U = q + w tells us we cannot create or destroy energy, but it can be
transferred in and out of the system.
T1 > T2
T1 T2
Object 1 Object 2
TEMPERATURE – an indication of heat content. During a change in

• objects at same T do not exchange heat energy. phase change, there
is no change in
• if T’s are different, energy (heat) flows from high T to low T. temperature.
• energy flow determined by molecular motions.
THERMOCHEMISTRY (Chapter 6)
– a subset of thermodynamics
– study of the heat given off or absorbed in a chemical reaction.
CHEMICAL REACTIONS AND ENERGY CHANGES Not all combustion

All chemical reactions are accompanied by an ENERGY CHANGE reactions result in
Chemical reactions may release heat to the surroundings, e.g., carbon dioxide and
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) (burning or combustion of natural gas) water
If heat is released (given off), the reaction is known as exothermic Freezing
This arises due to differences in bonding energy of reactants and products.
ALL combustion reactions are exothermic.
If heat is absorbed (taken in), the reaction is endothermic Melting

e.g., 6CO2(g) + 6H2O(l) → C6H12O6(s) + 6O2(g) (photosynthesis)
We will return to this when looking in detail at chemical reactions.

Note: The amount of heat depends on the size of the system.
(This is an EXTENSIVE property, like mass, V and n.)
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SIGN CONVENTION FOR HEAT PROCESSES NOTES:
PROCESS SIGN
Heat absorbed BY the system FROM the surroundings (endothermic) +
Heat absorbed FROM

____ the system ____
BY the surroundings (exothermic) –
Most reactions are run under constant pressure conditions (including biological
processes). The heat given off (or absorbed) at constant pressure is known as the
ENTHALPY change, and is denoted by the symbol, ∆H
ENTHALPY - is a measure of the difference in heat content, H,

between final and initial states (e.g., products and reactants).
i.e., ∆HRxn = Σ ∆Hproducts – Σ ∆Hreactants = qp = heat flow
Another name for heat content is ENTHALPY.
EXOTHERMAL and ENDOTHERMIC PROCESSES

Reactants
Enthalpy ∆HRxn < 0 Hand cold when
(heat released) you touch ice -
EXOTHERMIC EXOTHERMIC
Products
Water vapour
Products condenses on a
Enthalpy ∆HRxn > 0 cold pipe -
(heat absorbed) EXOTHERMIC
ENDOTHERMIC
Reactants
Remember:
• Heat changes at constant P are equal to the change in ENTHALPY
• If heat is given off, the rxn is EXOTHERMIC (∆H is negative)
• If heat is absorbed, the rxn is ENDOTHERMIC (∆H is positive)
We can measure this heat change through the science of calorimetry.
Aside: Calorimetry is derived from the Latin calor meaning heat and the Greek metry
meaning to measure. It is the science that deals with the measurement of the
quantities of heat in bodies that may be generated (exothermic process), consumed
(endothermic process) or simply dissipated by a sample. There are numerous
methods to measure such heat, and since calorimetry's advent in the late 18th
century, a large number of techniques have been developed.
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CALORIMETRY NOTES:
– measurement of the quantities of heat in bodies.
Experimentally, we need to:
• measure temperature change during a reaction, then
• convert that change in temperature to change in energy.
How?
HEAT CAPACITY (C) – energy required to raise the temperature of a substance Spacing of Celsius and
Kelvin units are the same
by 1C° or 1 K unit, i.e., C = q/∆T
YOU should distinguish between:
A) Heat Capacity (C) – energy required to raise a substance by 1C° or
1 K unit. Units: J∙K–1
B) Molar Heat Capacity ( C or c) – energy needed to raise 1 mole through
1C°or 1 K unit (or the heat capacity per mole).
Units: J∙K–1∙mol–1
C) Specific Heat (s, CSP or CS) – amount of energy to raise 1 gram through
1C° or 1 K unit (or the heat capacity per gram of substance).
Units: J∙g–1∙K–1 e.g., H2O(l) Specific Heat = 4.184 J∙g–1∙deg–1
Hence, q = C × ∆T = n × C × ∆T = mass × s × ∆T s = specific heat

Note: Don’t memorize 3 separate equations.
Simply match up the units to arrive at a final answer in Joules.
In calorimetry∙ the idea is to ISOLATE the SYSTEM from the SURROUNDINGS.

e.g. "Coffee–Cup" Calorimeter – refer to Figure 6.15 in text
To measure heat given off (or absorbed) by the chemical reaction:
• q = C∆T (calculate this usually)
• C – know this for the vessel and water (sometimes given together,
sometimes separately).
• ∆T – measure this
You will use a coffee-cup calorimeter in the first “wet” lab this semester.
Note: Heat released in the reaction is equal to the heat gained by the surroundings,
i.e., qSystem + qSurroundings = 0
therefore, qSystem = –qSurroundings = qRxn
qRxn = – (qsolution + qcalorimeter) = ∆H (since @ constant P) ∆H = -q(surroundings)
HEAT OF SOLUTION
- enthalpy change associated with dissolution of 1 mole solid:
i) take known mass of water at temperature, T1
ii) add mass of solid, dissolve and measure temperature T2
iii) calculate the change in temperature: ∆T = T2 – T1 = TFinal – TInitial
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Example – Dissolution of a solid (KF) in water: NOTES:
Exactly 1.23 g KF (s = 0.84 J∙g–1∙deg–1) is dissolved in 10.0 g H2O (s = 4.184 J∙g–1∙
deg–1). The H2O temp rises from 23.2 to 33.1°C. What is heat of solution per mole
for KF? (MM KF = 58.1 g mol–1)
KF dissolves in the water and liberates heat which warms the solution.
Energy = Heat gained by water + Heat gained by KF
Energy = q(H2O) + q(KF)
Energy = [mass x s(H2O) x ∆T] + [mass x s(KF) x ∆T)
= (4.184 J/gdeg x 10.0 g x 9.9 deg) + (0.84 J/gdeg x 1.23 g x 9.9 deg)
= 414 + 10.2
= 4.2 x 10^2 Joules (for 1.23 g)
MM(KF) = 58.1 g/mol, n(KF) = 0.02117 1 mole will evolve = 2.0 x 10^4 J
0.02117 mol evolve 4.2 x 10^2 J or 2.0 x 10 kJ/mol of heat is produced
q(Rxn) = ∆H(sol’n) = -2.0 x 10 kJ/mol
Note the size of q(KF) versus q(H2O)!
In many cases, we will just assume the specific hear of water is very close
to that of the solution and simplify this calculation to “Energy = q(H2O)”.
MM for KF = 58.1 g/mol, therefore # moles of KF added =
1 mole of KF would therefore evolve _______________________ of heat.
Example 2 – Transfer of heat (no chemical reaction):

50.0 g Cu (c = 24.5 J K–1 mol–1) is heated to 100°C and then placed in 250 g H2O
(s = 4.184 J g–1K–1) at 0.0°C. What is final temp of H2O (in °C)?
# moles of copper = 50.0 g / (63.66 g/mol)
= 0.787 moles
Let Tf(°C) represent the final temperature
Loss of heat from copper = Gain of heat in water
- (c x mol x ∆T) = C(s) x mass x ∆T
- [(24.5 J/Kmol) (0.787 mol) x ((T(ƒ) - 100) deg) = 4.184 J/gdeg x 250g x ((T(ƒ) - 0.0) deg)
1928 - 19.3 T = 1046 T
T = 1.81˚C
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Bomb Calorimeter (refer to Figure 6.16) NOTES:
• carries out combustion reactions at constant volume conditions
• the heat produced raises the temperature of the bomb and the
surrounding liquid (the bomb is usually placed in a water bath).
• Sometimes we evaluate the heat capacity of the bomb and the water
separately (i.e., qtotal = qbomb + qwater bath) and sometimes the heat capacity
for the entire calorimeter (bomb + water bath) has been determined
experimentally. You must read the question carefully to determine which
case you have.
Example:
Exactly 1.00 g of (CH3)2N2H2 (MM = 60.1 g/mol) is burned in a bomb calorimeter
with a heat capacity = 1840 J∙deg–1. A 5.00 kg water bath rises in temperature from
24.62 to 26.07°C. Calculate the energy released when 1 mole is burned.
Total heat produced = warms bomb + warms water bath

= (1840 J/deg x 1.45 deg) + (4.184 J/gdeg x 5x10^3g x 1.45 deg)
= 2668 + 30334
= 33002 J
33.0 kJ of heat is evolved by 1.00 g or 0.01664 mol
1 mol evolves 33.0/0.0166 = 1.98 x 10^3 kJ
1.98 x 10^3
1 mole of (CH3)2N2H2 evolves ____________________________ kJ of heat energy.
EXTRA PROBLEMS TO TRY
Solution is mainly dilute, so q
Problem 1: is going to be closer to water
50.0 mL dilute AgNO3 is added to a solution with OH– ions in a coffee cup calorimeter.
Ag2O precipitates and the temperature of the liquid goes from 23.78 to 25.19°C. Assume Since we are calculating
that the mixture has the same specific heat as water. Calculate "qsurr" for a mass of 150.0 g. q(surr), then reaction is
exothermic because it gives
Is the reaction exothermic or endothermic? off heat to the system
Answer: qSurroundings = 885 Joules
Rxn exothermic (temp rose).
Problem 2:
A 48.9 g sample of metal at 95.72°C is added to 43.58 g H2O at 23.84°C. The final
temperature of the metal + water is 28.37°C. What is the metal’s specific heat in J∙g–1∙deg–1?
Answer: s = 0.251 J∙g–1∙deg–1
Problem 3:
When ice at 0°C melts to liquid H2O, it absorbs 334 J per gram. The specific heat of water
is 4.184 J∙g–1∙deg–1. Suppose the heat needed to melt a 35.0g ice cube is absorbed from Once we get to Tƒ, we have
to make sure we reach full
water (0.210 kg) in a calorimeter at 21.0°C. What is the final water temperature? [This is equilibrium
the kind of calculation that all experienced party givers do before throwing a party!]
0˚C —> 0˚C Answer: TFinal = 6.6°C
q(ice melting) = -q(water cooling from 21˚C)
(35.0g x 4.184J/gdeg x {Tƒ - 0˚C (210g x 4.184J/gdeg x {Tƒ - 7.7˚C})
35g x 334J/g = - (210g x 4.184J/gdeg x {Tƒ - 21.0˚C}) 7 Tƒ = 6.6˚C
11690 J = -878.64Tƒ + 18451.44
Tƒ = 7.7˚C
0 —> 7˚C 7.7˚C —> Tƒ
WHAT ABOUT WORK? NOTES:
The first law of thermodynamics states that the change in the internal energy is
dependent upon the flow of heat, but is also depend on WORK.
WORK – the energy exchange that results when a force moves an
object through a distance.
EXAMPLES OF WORK
Mechanical: w = force × change in distance = F × ∆x = m × a × ∆x
Units: (mass) × (acceleration) × (distance) = kg•m2 •s-2 = N•m = Joule (J)
Electrical: w = charge × electric potential difference = Q × ∆E
Units: (coulombs) × (volts) = Joule
Note: We will look at this kind of work when we discuss electrochemistry later on in the course.
COMPRESSION/EXPANSION or P-V WORK (see Figs 6.5 & 6.6)

At a CONSTANT extension pressure, Pext., the work (in Joules) done BY the
surroundings ON a gas (i.e., system) is given by
w = force × distance = F × ∆x
w = F/A × A × ∆x = Pext. × A × ∆x
where the gas is compressed a distance ∆x by a pressure, Pext.
But, A × ∆x can be represented by the volume decrease, or,
w = Pext. ∆V where ∆V = V2 – V1
Compression: work is done ON the system BY the surroundings

Our definition says work is to be positive because for a gas to be
compressed, energy is added to the system, i.e., the surroundings
does work on the system.
So our relationship must be: w = – Pext.∆V
Expansion work is negative since energy leaves the system as the
system does work on the surroundings.
Pressure-Volume (or P-V) work is the most common type of work
encountered in chemical systems.
UNITS FOR ENERGY

1 J = 1 kg•m2•s-2 (SI definition) i.e., mass × velocity2
Note: 1 Pa = 1 N•m-2 = 1 kg•m-1•s-2 ∴1 J = Pa•m3
Hence P∆V → Pa•m3 = Joule
An older unit still in use is the “calorie”, where 1 cal = 4.184 J (by definition)
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EXAMPLE: Calculate the work at 25°C and 1.00 atm for NOTES:
a) CO2(g) + NaOH(s) → NaHCO3(s)
b) 2O3(g) → 3O2(g)
Consider:
– only PV work, Usually the case in first year
– that the gases behave ideally (i.e., follow the ideal gas law) and chem
– the equations represent the amounts in moles.
First determine the volume of the CO2(g), then determine the work done.
Definition of Work: w = –P∆V
Ideal Gas Law: PV = nRT
∴ P∆V = ∆nRT and w = –∆ngasRT
In a), we move from 1.00 mole of gaseous CO2 on the reactant side to 0 moles of
gas on the product side. Therefore, ∆ngas = ngas(Products) – ngas(Reactants)
No gas on right hand side
∆ngas = 0 – 1 = –1 mole
∴w = –∆ngasRT = -(-1 mol)(8.314 J·mol–1·K–1)(298K)
w = +2480 Joules
Work is done ON the system BY the surroundings. This is an example of a
compression. Work done is then positive, i.e., the system gains energy.
In b), we move from 2 moles of gaseous O3 on the reactant side to 3 moles of O2 on

the product side, i.e., ∆ngas = 3 – 2 = 1 mole & w = -2480 J. Work is done BY the
system ON the surroundings. This is an example of an expansion. Work done is
then negative, i.e., the system losses energy.
QUESTIONS:
1) A gas sample is heated in a cylinder using 550 kJ of heat. A piston
compresses the gas, doing 700 kJ of work. What is the change in internal
energy of the system?
∆U = q + w
= + 550 kJ + 700 kJ
= 1250 kJ
2) Calculate the work done when 6300 L of an ideal gas (initially at 1.00 atm)
is compressed (at constant T) by a constant pressure of 1.40 atm to a final
volume of 45L.
w = -P∆V
= - (1.40 atm) (45 L - 6300 L)
= + 8800 atm•L
Note: The gas constant R = 8.314 J K-1 mol-1 = 0.0821 L•atm K–1•mol–1
w = +8800 atm•L x 101.33 J/atm•L 9
= 890 kJ
SIGN CONVENTION FOR WORK and HEAT PROCESSES NOTES:
PROCESS SIGN
Work done BY the system ON the surroundings (expansion) –
Work done ____

ON the system ____
BY the surroundings (____________)
COMPRESSION +
Heat absorbed BY the system FROM the surroundings (endothermic) +
Heat absorbed FROM

____ the system ____
BY the surroundings (____________)
EXOTHERMIC –
• if w and q are positive, they tend to increase U of the system

• work done by the system is a reduction in U, hence negative.
INTERNAL ENERGY & ISOTHERMAL EXPANSIONS

• Internal energy of an ideal gas depends only on its temperature.
• To change the temperature of a gas, the internal energy must be changed by
doing work on it or transferring energy to it, i.e., ∆U = q + w.
• When a gas expands, the forces due to pressure push the container walls Work and heat are
back, so the gas is doing work. Change in w is negative. dependent on the paths
• For an isothermal (i.e., ∆T = 0) expansion of an ideal gas, ∆U = 0 because

the kinetic energy of the gas is related to its temperature (which here is If you integrate -P∆V,
unchanged) and the potential energy is related to bonding and structure you can find the
(which here is unchanged). maximum work
• Since ∆U = q + w = 0, ∴ w = –q. The system does w joules of PV-work

and absorbs an equivalent amount of heat q = –w.
HEAT CHANGES IN REACTIONS

a) Reactions at Constant Volume, i.e., a sealed container
System cannot expand or compress (∆V = 0), so the work is zero, i.e., w = 0
Using the First Law of Thermodynamics, ∆U = q + w;
∴At constant volume, qV = ∆U (e.g., in a bomb calorimeter) Sub “v” means constant volume
i.e., at constant volume (say in a sealed, “bomb” calorimeter), the
increase/decrease in internal energy corresponds to the heat
supplied/absorbed by the surroundings. Therefore the molar heat capacity ,
c, becomes: cv = qv/∆T = ∆U/∆T
b) Reactions at Constant Pressure, i.e., open to the atmosphere

The heat will cause the volume to change, i.e., ∆V ≠ 0
Some work will be done, e.g., pushing back the atmosphere
i.e., w = –Pext.∆V
Hence, ∆U = q – Pext.∆V qp = ∆U + Pext.∆V = ∆H
OR
∴At constant pressure, qp = ∆Η
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Most reactions run under constant pressure (including biological processes). NOTES:
We can measure this heat change with a coffee-cup calorimeter (refer to
page 239). When dealing with calorimetry measurements at constant
pressure, the molar heat capacity becomes: cp = qp/∆T = ∆H/∆T
Therefore, heat capacities give the rate of change of U and H with T.
∆U and ∆H are STATE functions. (q and w are not!)
Final
X
Height
X Initial
∆HEIGHT = HEIGHTFinal – HEIGHTInitial

A state function for a system depends on the differences between the final
and initial state ONLY, NOT on the pathway. This will become important
later when we discuss Hess’ Law.
HOW DO ∆H and ∆U COMPARE FOR A REACTION?

∆H = ∆U + ∆(PV)
For reactions at constant P, the above equation becomes:
∆H = ∆U + P∆V OR ∆H – ∆U = –w OR ∆U – ∆H = w
i.e., the difference between the change in internal energy and the enthalpy is the P∆V = - W
amount of work that needs to be done to make room for the products of the reaction. V∆P ≠ -W
For reactions at constant V, ∆H = ∆U + V∆P Note: V∆P ≠ w
Volume or pressure changes in solids and liquids are very small. Hence, for
processes involving only solids or liquids, ∆H is similar to ∆U.
For processes involving ideal gases at constant T, the equation PV = nRT will let us
calculate the volume or pressure change, i.e.,
∆(PV) = ∆(nRT)
P∆V = ∆nRT or V∆P = ∆nRT
i.e., ∆n = moles of gaseous products minus moles of gaseous reactants.
∴ ∆H = ∆U + ∆nRT
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Example: NOTES:
–1
At 298 K, CH4(g) + 2O2(g) → CO2(g) + 2H2O(l), ∆HRxn = –890.6 kJ mol
What is ∆URxn? normal lab case
q+w q(p) = ∆H
∆URxn = = ∆H - P∆V = -890 kJ/mol
= ∆H - ∆nRT
Could calculate the actual volume change from PV = nRT.
Not necessary (in this case), since we can use P∆V = ∆nRT.
∆n = 1 - 3
= -2 moles of gases
∆U = (-890kJ) - (-2)(8.314 x 10^3 kJ/molK) x 298 K
= -890 kJ + 4.96 kJ
=-885 kJ
Net result is a shrinking volume (compression), therefore work done by

____________________
system on _________________________.
surroundings
At 25°C, RT = 8.314 JK-1 mol–1 × 298K ≈ 2.5 kJ mol-1, therefore, ∆HRxn and ∆URxn
are not that far apart in value.
PROBLEM:
When an ideal gas expands at constant temperature (i.e., isothermal expansion), ∆U is zero.
Consider 1.00 L of an ideal gas initially at 9.00 atm and 15°C.
(a) Calculate q and w if the gas expands isothermally against a pressure of 1.00 atm.
(b) Calculate q and w if the gas expands isothermally first against a pressure of 3.00 atm.
And then against 1.00 atm.
(c) Calculate q and w if the gas expands isothermally first against a pressure of 3.00 atm,
then 2.00 atm and then against 1.00 atm.
(d) Comment on the results.
Answers:
a) q = –w = +0.810 kJ
b) w1 + w2 = –1.216 kJ
q1 + q2 = +1.216 kJ
c) w = w1 + w2 + w3 = –1.368 kJ
q = q1 + q2 + q3 = +1.368 kJ
d) The conclusion is that you would get
the maximum amount of work done
on the surroundings by doing the
expansion in an infinite number of
very small steps.
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Clicker Questions
1. Label the following process as exothermic or endothermic:
a) Your hand gets cold when you touch ice.
b) Water vapour condenses on a cold pipe.
2. Which of the following is (are) TRUE? cooler

a) A thermally isolated rxn vessel becomes warmer when an endothermic reaction occurs.
b) An exothermic reaction is characterized by a negative value of ∆H at constant P.
c) Heat is evolved when an exothermic reaction occurs. Evolved: energy is released
A) a only B) b only C) a & b only D) b & c only E) a, b, & c
3. For the reaction: ½A2(aq) + ½B2(aq) → AB(aq); ∆H° = -265 kJ/mol, if solutions A2 and B2,
starting at the same temp., are mixed in a coffee-cup calorimeter, the reaction that occurs is
A) Exothermic and T of the resulting solution rises.
B) Endothermic and T of the resulting solution rises.
C) Exothermic and T of the resulting solution falls.
D) Endothermic and T of the resulting solution falls.
4. Two different metals of equal mass with different specific heat capacities absorb the same
amount of heat. Which undergoes the smallest change in temperature?
A) metal with higher specific heat capacity doesn’t express a change as dramatically
B) metal with lower specific heat capacity
C) Because they have equal mass, both metals undergo the same change in temperature.
5. A 50.0 g sample of water at 80°C is added to a 100.0 g sample of water at 20°C. The final
temperature of the water should be
A) between 20°C & 50°C. B) 50°C. C) between 50°C & 80°C.
expansion = -w
6. Calculate the work needed to make room for products in the combustion of 1 mole of C3H8(g)
to CO2 and water vapour where reactants and products are brought to STP.
A) +2.48 kJ B) +2.27 kJ C) –2.27 kJ D) –2.48 kJ E) no work is required
7. Calculate the change in internal energy for a system that does 500 kJ of work on the
surroundings when 300 kJ of heat are absorbed by the system.
A) – 800 kJ B) – 200 kJ C) 0 kJ D) +50 kJ E) +75 kJ
5. - q (50.0 g H2O @ 80˚C = q(100.0g H2O @ 20˚C)
- [50.0g x 4.184 J/gdeg x (T(ƒ) - 80) deg] = 100.0g x 4.184 J/gedeg x (T(ƒ) - 20)deg
- T(ƒ) - 80 = 2(Tƒ - 20)
-Tƒ + 80 = 2Tƒ - 40
120 = 3Tƒ
Tƒ = 40˚C
6. C3H8(g) + 5O2(g) —> 3CO2(g) + 4H2O(g)
w = -∆n(gas)RT
∆n(gas) = (3+4) - (1+5)
= 1 mol
w = -(1)R(273)
= -2.27 kJ
13
– PART 2 –
NOTES:
Thermochemical Equations
A chemical equation may look like the following: CH4 + 2O2 → CO2 + 2H2O
A THERMOCHEMICAL equation looks like the following:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l), ∆H° = -890kJ
What is different?
__________________________
STATES specified in a thermochemical equation
∆H˚ VALUES are given in kJ & a sign is specified (+/-)
∆H
________________ is a stoichiometric term!
Convention: Measurements usually made at 25°C (298K). Temperature always has
to be specified
The "°" symbol refers to “STANDARD CONDITONS”:
• pure reactants & products at 1 atm of pressure (actually 1 bar ≈ 105 Pa)
• solids & liquids are in their most stable form, known as "standard state"
• solutes are 1 mol∙L-1. pH = 0 (log 1 = 0)
• temperature must be specified. Note: T = 25°C is commonly used,
BUT is NOT included within the definition of "standard" conditions.
The above thermochemical equation tells us that when 1 mole of methane is burned
completely in air to give CO2 gas and liquid water, 890 kJ of energy is released.
A typical ENDOTHERMIC rxn: CaCO3(s) → CaO(s) + CO2(g), ∆H° = +178 kJ

i.e., we must supply 178 kJ of energy to convert 1 mole CaCO3(s) to CaO(s) & CO2(g).
Some Simple Thermochemical Rules & Laws

RULE 1:
Thermochemical equations describe the energy changes associated
with 1 mole of something.
e.g., We saw above that the ∆H° for combustion of 1 mole CH4
at 298 K was –890 kJ (or –890 kJ/mole).
When a thermochemical equation is multiplied by any factor,
the value of ∆H° is also multiplied.
Question: How much energy is released if we burn 1.00 L CH4(g) at

1.01×105 Pa and 25°C?
14
The first thing we should ask ourselves is "How many moles of CH4 are NOTES:
present in 1.00 L at 1.01×105 Pa & 25°C?"
# moles of CH4(g) at 1.01×105 Pa, 1.00 L and 25°C:

Since PV = nRT, therefore n = PV/RT
Note: If P in Pa and V is m3, then use R = 8.314 Pa∙m3∙K–1∙mol–1
If P in kPa and V is L, then us R = 8.314 kPa∙L∙K–1∙mol–1
n=
PV (1.01× 10 Pa)
=
5
(
1 kPa
1000 Pa)(1 L)
=
RT (8.314 kPa ⋅ L ⋅ K ⋅ mol )(298K)
–1 –1
Based on the thermochemical equation given earlier, 1 mole CH4

890
evolves __________ kJ, therefore 4.08×10–2 moles of CH4 evolves
4.08×10–2 mol × __________
890 kJ/mol = 36.3 kJ
RULE 2:
CHANGE THE SIGN of ∆H
If we REVERSE the direction of a reaction, we __________________
e.g., CaCO3(s) → CaO(s) + CO2(g), ∆H° = +178 kJ
CaO(s) + CO2(g) → CaCO3(s), ∆H° = __________
-178 kJ
RULE 3:
Thermochemistry (and Thermodynamics) is only interested in energy
differences between initial and final states. It is not concerned with HOW
(i.e., "by what mechanism") a reaction takes place. All this means is that we
can add (or subtract) thermochemical equations to produce other equations.
Hess's Law: Thermochemical equations can be added (or subtracted) to

yield other thermochemical equations. (more on this later)
THERMOCHEMISTRY OF CHANGE
1. Changes of Physical State
e.g., solid → liquid → gas
A. Enthalpy of Fusion, ∆𝑯𝑯°𝒇𝒇𝒇𝒇𝒇𝒇 : the enthalpy change when we fuse (i.e., melt)
1 mole of something.
e.g., 1 mole solid → 1 mole liquid
H2O(s) → H2O(l); ∆𝐻𝐻𝑓𝑓𝑓𝑓𝑓𝑓
°
= +6.0 kJ/mol ALWAYS +
0°C 0°C
Note: Temperature remains constant while the process is occurring.
∆H°fus is always a POSITIVE value; energy has to be added to weaken

forces (intermolecular) and cause the solid to flow.
15
For the reverse process, i.e., freezing: NOTES:
H2O(l) → H2O(s); ∆𝐻𝐻𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
°
= – 6.0 kJ/mol
0°C 0°C Note opposite sign.
i.e., In general, ∆H°Reverse process = –∆H°Forward process
B. Enthalpy of Vaporization, ∆𝑯𝑯°𝒗𝒗𝒗𝒗𝒗𝒗 enthalpy change when we vapourise

1 mole of liquid to gas. ∆H°vap is always a POSITIVE value.
ALWAYS +
e.g., H2O(l) → H2O(g); ∆𝐻𝐻𝑣𝑣𝑣𝑣𝑣𝑣
°
= +40.7 kJ/mol
100°C 100°C °
Note this value is much larger than 𝐻𝐻𝑓𝑓𝑓𝑓𝑓𝑓 .
What is the name for the reverse process? (condensation)
Heating Curve for Water
boiling point ∆H°vap gas

100°C
Temp
(°C) liquid
∆H°fus
0°C melting point
solid
Time heat supplied
C. Enthalpy of Sublimation, ∆𝑯𝑯°𝒇𝒇𝒇𝒇𝒔𝒔 :

– enthalpy change when we sublime 1 mole solid → 1 mole gas.
° ALWAYS +
∆𝐻𝐻𝑓𝑓𝑓𝑓𝑠𝑠 is always a POSTIVE value.
e.g., H2O(s) → H2O(g); ∆𝐻𝐻𝑓𝑓𝑓𝑓𝑠𝑠

°
= +46.7 kJ/mol
Note: ∆H°sub = ∆H°fus + H°vap ...can do this since enthalpy is a state function, i.e.,

°
= 6.0 kJ/mol
+ H2O(l) → H2O(g); ∆𝐻𝐻𝑣𝑣𝑣𝑣𝑣𝑣
°
= 40.7 kJ/mol
H2O(s) → H2O(g); ∆𝐻𝐻𝑓𝑓𝑓𝑓𝑠𝑠
°
= 46.7 kJ/mol (See Rule#3 above.)
What is the name for the reverse process? (deposition)
16
– PART 2 –
NOTES:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l), ∆H° = -890kJ
What is different?
__________________________
∆H
to be specified


RULE 1:

1.01×105 Pa and 25°C?
14
– PART 2 –
NOTES:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l), ∆H° = -890kJ
What is different?
__________________________
∆H
to be specified


RULE 1:

1.01×105 Pa and 25°C?
14
The first thing we should ask ourselves is "How many moles of CH4 are NOTES:
present in 1.00 L at 1.01×105 Pa & 25°C?"
# moles of CH4(g) at 1.01×105 Pa, 1.00 L and 25°C:

Since PV = nRT, therefore n = PV/RT
Note: If P in Pa and V is m3, then use R = 8.314 Pa∙m3∙K–1∙mol–1
If P in kPa and V is L, then us R = 8.314 kPa∙L∙K–1∙mol–1
n=
PV (1.01× 10 Pa)
=
5
(
1 kPa
1000 Pa)(1 L)
=
RT (8.314 kPa ⋅ L ⋅ K ⋅ mol )(298K)
–1 –1
Based on the thermochemical equation given earlier, 1 mole CH4

890
evolves __________ kJ, therefore 4.08×10–2 moles of CH4 evolves
4.08×10–2 mol × __________
890 kJ/mol = 36.3 kJ
RULE 2:
CHANGE THE SIGN of ∆H
If we REVERSE the direction of a reaction, we __________________
e.g., CaCO3(s) → CaO(s) + CO2(g), ∆H° = +178 kJ
CaO(s) + CO2(g) → CaCO3(s), ∆H° = __________
-178 kJ
RULE 3:
Thermochemistry (and Thermodynamics) is only interested in energy
differences between initial and final states. It is not concerned with HOW
(i.e., "by what mechanism") a reaction takes place. All this means is that we
can add (or subtract) thermochemical equations to produce other equations.
Hess's Law: Thermochemical equations can be added (or subtracted) to

yield other thermochemical equations. (more on this later)
THERMOCHEMISTRY OF CHANGE
1. Changes of Physical State
e.g., solid → liquid → gas
A. Enthalpy of Fusion, ∆𝑯𝑯°𝒇𝒇𝒇𝒇𝒇𝒇 : the enthalpy change when we fuse (i.e., melt)
1 mole of something.
e.g., 1 mole solid → 1 mole liquid
°
= +6.0 kJ/mol ALWAYS +
0°C 0°C
Note: Temperature remains constant while the process is occurring.
∆H°fus is always a POSITIVE value; energy has to be added to weaken

forces (intermolecular) and cause the solid to flow.
15
For the reverse process, i.e., freezing: NOTES:
H2O(l) → H2O(s); ∆𝐻𝐻𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
°
= – 6.0 kJ/mol
0°C 0°C Note opposite sign.
i.e., In general, ∆H°Reverse process = –∆H°Forward process
B. Enthalpy of Vaporization, ∆𝑯𝑯°𝒗𝒗𝒗𝒗𝒗𝒗 enthalpy change when we vapourise

1 mole of liquid to gas. ∆H°vap is always a POSITIVE value.
ALWAYS +
e.g., H2O(l) → H2O(g); ∆𝐻𝐻𝑣𝑣𝑣𝑣𝑣𝑣
°
= +40.7 kJ/mol
100°C 100°C °
Note this value is much larger than 𝐻𝐻𝑓𝑓𝑓𝑓𝑓𝑓 .
What is the name for the reverse process? (condensation)
Heating Curve for Water
boiling point ∆H°vap gas

100°C
Temp
(°C) liquid
∆H°fus
0°C melting point
solid
Time heat supplied
C. Enthalpy of Sublimation, ∆𝑯𝑯°𝒇𝒇𝒇𝒇𝒔𝒔 :

– enthalpy change when we sublime 1 mole solid → 1 mole gas.
° ALWAYS +
∆𝐻𝐻𝑓𝑓𝑓𝑓𝑠𝑠 is always a POSTIVE value.
e.g., H2O(s) → H2O(g); ∆𝐻𝐻𝑓𝑓𝑓𝑓𝑠𝑠

°
= +46.7 kJ/mol
Note: ∆H°sub = ∆H°fus + H°vap ...can do this since enthalpy is a state function, i.e.,

°
= 6.0 kJ/mol
+ H2O(l) → H2O(g); ∆𝐻𝐻𝑣𝑣𝑣𝑣𝑣𝑣
°
= 40.7 kJ/mol
H2O(s) → H2O(g); ∆𝐻𝐻𝑓𝑓𝑓𝑓𝑠𝑠
°
= 46.7 kJ/mol (See Rule#3 above.)
What is the name for the reverse process? (deposition)
16
2. Enthalpy Changes for Chemical Reactions NOTES:
A. Enthalpy of Combustion, ∆H°comb:
– enthalpy change when we burn 1 mole of something completely in O2.
e.g., C(s) + O2(g) → CO2(g); ∆H°comb = – 393.5 kJ
∆H°comb is always a NEGATIVE value,
because energy is always released (exothermic).
B. Enthalpy of atomization:
– ∆H° associated with the formation of 1 mole of ATOMS from its elements.
e.g., ½H2(g) → H(g); ∆H°atom = +218 kJ
∆H°atom is always a NEGATIVE POSITIVE value (as bonds are broken).
Note: The standard enthalpy of reaction, ∆H°Rxn, or standard "heat" of

reaction is a general description used to refer to any reaction.
HESS' LAW
(Refer to page 245 in 10th ed. text. – Section 6.7)
Hess' Law – ∆H° for an overall process is the sum of the ∆H°'s for
the individual steps of the process.
Thermochemistry (and thermodynamics) is only interested in the energy

differences between initial and final states. It doesn't matter how we got
there. Hence we can add (or subtract) thermochemical equations to produce
other thermochemical equations. (Thermochemical Rule # 3.)
Example:
Suppose we wanted to know ∆H°Rxn for Sn(s) + 2Cl2(g) → SnCl4(l), but you could
not find the value in any set of tables. But, you did find the following:
(a) Sn(s) + Cl2(g) → SnCl2(s); ∆H°Rxn = –350 kJ
(b) SnCl2(s) + Cl2(g) → SnCl4(l); ∆H°Rxn = –195 kJ
Can you manipulate these equations to arrive at the one we want?
If (a) is added to (b) you get:
Sn(s) + 2Cl2(g) → SnCl4(l), ∆H°Rxn = __________

-545 kJ
17
Example: Given the following data: NOTES:
3
N2(g) + O2(g) → N2O3(g) ∆H° = 83.7 kJ R1. flip equation
2
N2(g) + O2(g) → 2NO(g) ∆H° = 180.4 kJ ∆H˚ = -83.7 kJ
½N2(g) + O2(g) → NO2(g) ∆H° = 33.2 kJ
R2. divide by 2
what is ∆H° for the reaction: N2O3(g) → NO(g) + NO2(g) ∆H˚ = 90.2 kJ
A) –207.1 kJ D) +39.7 kJ
-R1 + 1/2R2 + R3
B) –39.7 kJ E) +207.1 kJ
C) +24.3 kJ
Extra Problem:
Given:
(a) ½ N2(g) + ½ O2(g) → NO(g); ∆H°Rxn = +90.4 kJ
(b) ½ N2(g) + O2(g) → NO2(g); ∆H°Rxn = +33.2 kJ
Calculate ∆H°Rxn for: 2NO(g) + O2(g) → 2NO2(g)
Ans: ∆H°Rxn= – 114.4 kJ
To use Hess's Law effectively we obviously need to have access to tables of ∆H°
values. Rather than write out full thermochemical equation for every ∆H°, we devise
a method (outlined below) which will allow you to deduce the
appropriate thermochemical equation.
STANDARD ENTHALPY OF FORMATION (∆H°f or ∆fH°)

The Standard Molar Enthalpy of Formation (or the standard heat of
formation) is the enthalpy change when we form ONE mole of a substance
from its ELEMENTS in their STANDARD STATES at 1.0×105 Pa (1 atm).
******************************************************************
Aside: Previous, we looked at the combustion reaction:
C(s) + O2(g) → CO2(g); ∆H°comb = – 393.5 kJ
This reaction also leads to the formation of CO2(g) in its standard state.
Hence, the heat of this reaction (–393.5 kJ/mol), which we noted as the heat
of combustion, is also the heat of formation of CO2(g), i.e., ∆H°f [CO2(g)]
= –393.5 kJ/mol.
******************************************************************
These ∆H°f values can be obtained for many, many compounds (see Appendix C:
Thermodynamic Quantities for Substances and Ions at 25°C).
18
∆H°f values can be negative (as seen above), positive or zero, e.g., NOTES:
Different forms of bromine ∆H°f (kJ/mol)
Br2(l) 0
Br2(g) 30.91
Br(g) 111.88
Note: The energy difference between Br2(g) and Br(g) corresponds
to the energy to break the Br-Br bond.
Allotropes of Carbon ∆H°f (kJ/mol)

C(s, graphite) 0
C(s, diamond) +1.897
You should be able to write an equation that defines a heat of formation.
Example: The heat of formation (∆H°f) for liquid ethanol, C2H5OH(l) is

–278 kJ/mol, write the thermochemical equation.
Step 1: → C2H5OH(l) (form 1 mole of the compound)
Step 2: C(s) + H2(g) + O2(g) → C2H5OH(l) (from its elements as reactants)
Step 3: 2C(s) + 3H2(g) + 1/2O2(g) → 1 C2H5OH(l) ∆H°f = -278 kJ (balance eq’n)
Note: For a pure element in its most stable form, at a chosen temperature
(usually 25°C), ∆H°f = 0 J at 1 atm.
WHY?
You’re getting the atom from the element itself so no chemical change!
O2(g) —> O2(g)
From a list of ∆H°f we can:

Calculate heats of other reactions
Calculate ∆H°f’s that are difficult to measure
In some cases, ∆H°f cannot be defined directly by writing an equation from the
elements. Therefore, we must combine other equations to get the desired products
(see below).
19
Question: The standard enthalpy of formation of sulfuric acid, H2SO4(l), refers to NOTES:
the ∆H° of which of the following reactions?
A) H2SO4(l) → H2(g) + S(s) + 2O2(g)
B) H2(g) + S(g) + 2O2(g) → H2SO4(l) Sulfur is always
C) H2SO4(l) → 2H(g) + S(s) + 4O(g) going to be a solid at
standard conditions
D) H2(g) + S(s) + 2O2(g) → H2SO4(l)
E) 2H(g) + S(g) + 4O(g) → H2SO4(l)
Problem:
Given ∆H°f values for H2O(l) = –286 kJ/mol
H2O(g) = –242 kJ/mol
Calculate ∆H°vap for H2O(l)
We want H2O(l) → H2O(g), ∆H°vap = ?
We are given:
a) H2(g) + 1/2O2(g) —> H2O(l), ∆H = -286 kJ
b) H2(g) + 1/2O2(g) —> H2O(g), ∆H = -242 kJ
Therefore H2O(l) —> H2O(g), ∆H˚(vap) = 286 + (-242) = 44 kJ
Apply Hess's Law: H2O(l) → H2O(g), ∆H°vap = __________

44.0 kJ
44.0
44.0
∴ ∆H°vap for H2O(l) is ____________ kJ/mol

i.e., 44.0 kJ must be SUPPLIED to evaporate 18.0 g H2O(l) → 18.0 g H2O(g)
What we have seen is an example of a general rule IF we have complete ∆H°f data:
∆H°rxn = Σn∆H°f (products) – Σn∆H°f (reactants)

This equation is only useful if we have ALL the ∆H°f data,
whereas Hess’ Law ALWAYS works!
ANOTHER APPROACH:
2CH3CHO(l) → C2H5OH(l) + CH3COOH(l)
ethanal ethanol ethanoic acid
(acetaldehyde) (acetic acid) Elements
Envisage a hypothetical process: Step 1 Step 2

Step 1: Reactants → Constituent Elements
Step 2: Constituent Elements → Products Reactants → Products
20
For Step 1: ∆H° = sum of –∆H°f for all reactants NOTES:
For Step 2: ∆H° = sum of ∆H°f for all products
Combining the two: ∆H°rxn = Σn∆H°f (products) – Σn∆H°f (reactants)

Returning to the original equation:
2CH3CHO(l) → C2H5OH(l) + CH3COOH(l)
Given
∆H°f values –192.3 –277.69 –484.5 kJ/mol
∆H°rxn = [–277.69 – 484.5] – [–192.3 × 2]
∆H°rxn = –377.6 kJ
Note: Watch to make sure you include the coefficients within the balanced equation
(e.g., 2CH3CHO) to arrive at the correct amount of energy.
Remember: Any equation showing the standard molar enthalpy of formation of a

compound must show the formation of 1 mole from the elements in their
standard states, e.g., ∆H°f (NH3) is –46.11 2 kJ/mol
The thermochemical equation is: ½N2(g) + 3/2H2(g) → NH3(g); ∆H°f = –46.11 kJ
When using ∆H°f values – you have two ways to choose from:
1) long way (Hess' law)
2) short way (using ∆H°f directly)
Question: Calculate the heat required to decompose limestone:

CaCO3(s) → CaO(s) + CO2(g)
You are given:
∆H°f [CaCO3(s)] = –1206.9 kJ/mol
∆H°f [CaO(s)] = –635.1 kJ/mol
∆H°f [CO2(g)] = –393.5 kJ/mol
1) The Long Way (Hess's Law):

First write out the three thermochemical equations for the three given
heats of formation:
a) Ca(s) + C(s) + 3/2O2(g) —> CaCO3(s), ∆H˚ƒ = -1206.9 kJ/mol
b) Ca(s) + 1/2O2(g) —> CaO(s), ∆H˚ƒ = -635.1 kJ/mol
c) C(s) + O2(g) —> CO2(g), ∆H˚ƒ = -393.5 kJ/mol
Then see how to manipulate each to arrive at needed thermochemical equation,

e.g., for the given reaction, CaCO3(s) appears on the LHS, therefore equation a)
must be reversed and the sign of ∆H°f [CaCO3(s)] changed to a positive value.
21
So, rewrite the equations to arrive at the final equation and add them up:
CaCO3(s) —> Ca(s) + C(s) + 3/2O2(g), ∆H˚ƒ = +1206.9 kJ/mol
+ Ca(s) + 1/2O2(g) —> CaO(s), ∆H˚ƒ = -635.1 kJ/mol
+ C(s) + O2(g) —> CO2(g), ∆H˚ƒ = -393.5 kJ/mol
__________________________________________________________
CaCO3(s) → CaO(s) + CO2(g); ∆H°Rxn = +178.3 kJ
2) The Short Way

The mathematics of the above problem really amounts to the same as,
∆H°rxn = Σn∆H°f (products) – Σn∆H°f (reactants)
In this case,
∆H°rxn = ((-635.1 + (-393.5)) - (-1206.9) kJ/mol
∆H°rxn =
∆H°rxn = +178.3 kJ
So, if you have ALL the ∆H°f data you can simply do it the short way (a shortcut around
writing down all the thermochemical equations). Note, however, Hess's Law works ALL
the time.
Problem 1:
Calculate ∆H°Rxn for the reaction CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
Ans: ∆H°Rxn = –891 kJ/mol
Problem 2:
Given
(a) 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(l); ∆H° Rxn = –1169 kJ
(b) 4NH3(g) + 3O2(g) → 2N2(g) + 6H2O(l); ∆H° Rxn = –1530 kJ
What is ∆H°f for NO(g)?
Ans: ∆H°f = +90.3 kJ/mol
Problem 3:
Given ∆H°f [C2H6(g)] = –85 kJ/mol; ∆H°f [H2O(l)] = –286 kJ/mol; ∆H°f [CO2 (g)] = –394 kJ/mol
Calculate how much energy is released when 1.00 g C2H6 (g) is burned in air at 25°C and
1.01 × 105 Pa. Ans: 1.00 g C2H6 evolves 51.9 kJ of energy upon combustion.
C2H6(g) + 7/2 O2(g) —> 2CO2(g) + 3H2O(l)
∆H˚Rxn = 2(-394) + 3(-286) - (-85) - 7/2(0)

= -1561 kJ/mol
1.00 g C2H6 —> 0.0332 mol C2H6
-1561 kJ/mol(mol C2H6) x 0.0332 mol = 51.9 kJ
22
Example from Nature: The Bombardier Beetle defends itself by "shooting" a hot solution
of benzoquinone at its enemies.
Reaction: C6H4(OH)2(aq) + H2O2(aq) → C6H4O2(aq) + 2H2O(l)

(a) Calculate ∆H°Rxn for this reaction given:
(i) C6H4(OH)2(aq) → C6H4O2(aq) + H2(g); ∆H°Rxn = +177 kJ
(ii) ½O2(g) + H2O(l) → H2O2(aq); ∆H°Rxn = + 94 kJ
(iii) H2(g) + ½O2(g) → H2O(l); ∆H°f = –286 kJ
Ans: –203 kJ
(b) Calculate the rise in temperature of 4.0 mg H2O produced by oxidation of 8.0 × 10–6
mol C6H4(OH)2.
Ans: ∆T = 97C° ---> hot stuff!
STANDARD ENTHALPIES OF FORMATION

NOTES:
OF IONS IN AQUEOUS SOLUTION
To deduce the ∆H°f values for all ions in aqueous solution, we needed a method
to separate the contributions of the ions.
SOLUTION: Define ∆H°f (H+, aq) = 0
****************************************************************
ASIDE: Consider the reaction: HCl(g) → H+(aq) + Cl–(aq)
∆H°Rxn = {∆H°f [H+(aq)] + ∆H°f [Cl–(aq)]} – {∆H°f [HCl(g)]}
(measured) (obtain) (known)
• ∆H°Rxn for this reaction is measured as –74.89 kJ/mol
• ∆H°f (HCl(g)) is known as – 92.31 kJ/mol
We can then write:

∆H°Rxn = {∆H°f [H+(aq)] + ∆H°f [Cl–(aq)]} – {∆H°f [HCl(g)]}
–74.89 = {∆H°f [H+(aq)] + ∆H°f [Cl–(aq)]} – (– 92.31)
{∆H°f [H+(aq)] + ∆H°f [Cl–(aq)]} = –167.20 kJ/mol
Although we can obtain the SUM this way, the separate contributions of the
two ions cannot be obtained by any experiment yet devised.
What to do?
23
SOLUTION: Define ∆H°f (H+, aq) = 0
Hence for the reaction: ∆H°f [Cl–(aq)]} =
Now that we have ∆H°f [Cl–(aq)]} we can get ∆H°f [Na+(aq)]} from an experiment
using NaCl(s) (i.e., NaCl(s) → Na+(aq) + Cl–(aq))
From similar experiments we can determine the values for other ions
(e.g., NaBr, KBr, etc.)
Therefore, we can deduce ∆H° f values for all other ions in aqueous solution.
*******************************************************************
Clicker Questions
1. Which is/are endothermic process(es)?

1. Combustion 1 mole burned completely in O2 A) 1 only
2. Fusion 1 mole solid —> 1 mol liquid B) 2 & 3 only
3. Vapourisation 1 mol liquid —> 1 mol gas C) 2, 3 & 4 only
4. Sublimation 1 mol solid —> 1mol gas D) 2, 3, 4 & 5 only
5. Atomisation Elements —> 1 mol of ATOMS E) All of the above!
2. Which of the following has (have) a non-zero enthalpy of formation value at 25°C & 1.00 atm?
a. O(g) A) a only
O2(g) is the standard state of
b. O2(g) B) b only oxygen at 1 atm, so it’s
c. O3(g) C) c only formation enthalpy is, by
definition, zero.
D) a and c only
E) a, b, and c
24
THERMO - PART 3
BOND ENERGIES IN COVALENT MOLECULES NOTES:
(Refer to section 9.11 in text)
Covalent Bonds – bonds resulting from the sharing of electrons between atoms.
e.g., :Cl– Cl: , H–C C–H, H–(C=O)–H
The distance between the atoms is the bond length (depends on the atoms).
Not all covalent bonds are equal – they involve different nuclei and different
electron distributions, (e.g., C–C, C=C, C C, etc.). Hence the energy to
break bonds can differ.
Bond Enthalpy (or Energy) (BE) or

Bond Dissociation Enthalpy (or Energy) (BDE), HBD
- energy required to BREAK a mole of bonds in the gas phase (does not hold
for liquid or solid state). Note: Products are neutral species NOT ions!
Is always large
- is ALWAYS POSITIVE, since enthalpy change is associated with breaking
a covalent bond (energy must be supplied).
- is a measure of the strength of a covalent bond.
BE can be defined as the enthalpy change ( HBD) for the dissociation of the
bond into its constituent atoms or free radicals in the gas phase.
e.g., H–H(g) 2H•(g); HBD = +436 kJ
i.e., to disrupt, break, pull apart, 1 mole of H–H bonds, we must provide 436 kJ.
We can then say that the bond enthalpy of H2 is 436 kJ.
Note: HBD = BE(H–H) = +436 kJ 2 Hf [H, g]
Hf [H, g] +436 kJ/mol 2 = 218 kJ/mol
Atomisation: process of
HBD also 2 HAtomisation for H division
Generally, BE are not as exact as Hf values,

since BE values come from average values.
What about F2(g), Cl2(g), Br2(g), N2(g), O2(g)? No Problem!

Cl2(g) 2 Cl(g), HBD = 242 kJ/mol
O2(g) 2 O(g), HBD = 498 kJ/mol
What about an O–H bond?

Use: H2O(g) 2H(g) + O(g); HRxn = 926 kJ
ONE mole of O–H bonds would require 926kJ/2 or ~_________
463 kJ.
25
What about C–H? NOTES:
Use: CH4(g) C(g) + 4H(g), HRxn = +1656 kJ
i.e., to break FOUR moles of C–H bonds costs 1656 kJ,
therefore bond enthalpy of C–H 1656 kJ / 4 414 kJ
Using BE’s ( HBD) and their Relationship to Hf

EXAMPLE: Estimate the H f for NH3 given HBD (N N) is 945 kJ, HBD (H–H)
is 436 kJ, and HBD (N–H) is 391 kJ. (Aside: Table 9–5 provides several values.)
Strategy: What equation do we want? 1/2 N2(g) + 3/2 H2(g) —> NH3
What we need to do is break the N N & H–H bonds and reform 3(N–H) bonds.
Atoms(g) Energy has to be put
Form Atoms:
N(g), 3H(g) in to get to the top.
Break H2:
3 [½H2(g) H(g)]
Form NH3: Correcting the sign
Break N2: H1 H2 – 3(N-H) bonds
½N2(g) N(g) Energy is released
when the atoms
become stable and
H f=?
complete their octet (a
½N2(g) + 3/2 H2(g) NH3(g) sound may also occur)
BEGIN HERE Elements Product END HERE
(most stable form) (1 mole)
H f (NH3) = H1 + H2
H f (NH3) = [½BE(N–N) + 3/2BE(H–H)] + [– 3BE(N–H)]
H f (NH3) = 1/2 (945) + 3/2 (436) - 3 (391)
H f (NH3) = – 46.5 kJ/mol (compare H f (NH3) = – 45.90 kJ from Appendix C)
GENERALISATION:
HRxn = (energy needed (+) to break bonds) + (energy released (–) when bonds formed)
OR
HRxn = BEReactant Bonds – BEProduct Bonds
26
________________________________________________________________________________ NOTES:
ASIDE: Same question but with different data:
Estimate the H f for NH3 given: N(g) H f = 472 kJ/mol
H(g) H f = 218 kJ/mol
BE(N–H) = HBD = 391 kJ/mol
Rxns for values given:
H f N, g = 472 kJ/mol; Rxn:
H f H, g = 218 kJ/mol; Rxn:
NH3(g) N(g) + 3H(g); HRxn =
H f(NH3) = – 47 kJ/mol
___________________________________________________________________________________________________
What about C–C? (there are no C–C molecules!)

Given:
H f (C2H6, g) = - 85 kJ,
BE of C–H = + 413 kJ,
BE for H2(g) = + 436 kJ,
H Atomisation (C, s) = + 720 kJ
Calculate a value for the C–C bond enthalpy. (Ans: BE (C–C ) 355 kJ/mol)
Atoms(g)
2C(g), 6H(g)
Break into atoms:

2 x ∆H˚atom 2C(s) 2C(g) Form C2H6:
[2 x 720] – [BDE (C-C) + 6 BDE(C-H)]
3H2(g) 6H(g)
[3 x 436]
H f = -85 kJ
2C(s) + 3H2(g) C2H6(g)
Elements Product
(most stable form) (1 mole)
∆H˚ƒ = [2 x ∆H˚atomC] + 3 x ∆H(Be(H-H)) - ∆H(Be(C-C)) - [6 x ∆H(Be(C-H))]
- 85 = 2(720) + 3(436) - BDE(C-C) - 6(413) kJ
BDE(C-C) = 355 kJ/mol
NOTE: Bond Dissociation Enthalpy values are for GASES ONLY

All reactants & products must be in the gaseous state to use BDE values alone; if
have solids or liquids, must use Hess’ Law to use BDE values with other values.
27
NOTES:
We can build up a table of bond enthalpies to use (refer to Table 9–5).
Typical Average Bond Energies (BE, HBD) (REF: 10th ed. values)
C–H 413 O–H 463 C=C 614
C–C 348 H–H 436 C C 839
C–N 293 etc. C=N 615
C–O 358 C=O 804
C–F 485 N=N 418
C–I 240 N N 945
For benzene, resonance causes the CC bond enthalpy to be 518 (~1 bond + ½). Note also
that 1 C C ≠ 3 C–C. Bond energies are useful in determining weak points in a molecule.
e.g., When CFC–11 is exposed to UV radiation in the stratosphere, the C–Cl bond (BE
~ 328 kJ/mol) breaks not the C–F bond (BE ~ 485 kJ/mol).
CFCl3(g) CFCl2(g) + Cl(g) then,
Cl(g) + O3(g) OCl(g) + O2(g)
Bond Lengths and Bond Enthalpies

Bond Bond length Bond enthalpy
C–N 1.47 Å or 147 pm 293 kJ
C=N 1.27 Å or 127 pm 615 kJ
C N 1.16 Å or 116 pm 891 kJ
In comparing single, double and triple bonds, we see that the

bond length grows shorter while the bond enthalpy gets larger.
Problems:
1. Given the following, determine a value for the N–N bond enthalpy in
hydrazine, N2H4(g) (a rocket fuel which is discussed on p. 255 (p. 251) in the text).
Heat of formation of liquid hydrazine is +51 kJ mol– 1
Heat of vaporisation of liquid hydrazine is +48 kJ mol–1
Bond Energies: N N is +942 kJ H–H is +432 kJ N–H is +386 kJ
Answer: 163 kJ/mol

2. Given the following (kJ) data, estimate a value for the CS bond enthalpy
in CS2(g). Note: CS2 is isostructural with CO2.
H(combustion) CS2(l) –1108, C(s) –393, S(s) –297;
H(atomisation) C(s) +711, S(s) +280 kJ
H(vaporisation) CS2(l) +27 kJ Ans: 562 kJ/mol
28
IONIC BONDING and LATTICE ENERGIES NOTES:
Refer to section 9.1 (Energy Involved in Ionic Bonding) in text
Ionic Bonds
– these result from a complete transfer of an electron
– formation of ionic solids from elements is an exothermic process.
e.g., Na + Cl Na+ + Cl– NaCl(s)
Let’s say we want to make NaCl(s) starting from its constituent elements.
5 STEP PROCESS:
1. Sublimation ( Hsub) of Na metal: Na(s) —> Na(g); ∆H1 = 108 kJ (∆H(sub))
2. 1st Ionisation ( 1) of Na(g): Na(g) Na+(g) + e–; H2 = 496 kJ
3. Dissociate (BDE) of Cl2(g): 1/2 Cl2(g) —> Cl(g); ∆H3 = 120 kJ (1/2 BDE)
4. 1st Electron Gain Enthalpy (EG1) for Cl(g): Cl(g) + e– Cl– (g); H4 = –349 kJ
5. Bring Na+(g) & Cl–(g) together: Na+(g) + Cl-(g) —> NaCl(s); ∆H5 = -781 kJ
(Energy is released in this process.)
Step 5 is the important step (energy wise) in forming the ionic solid and is known as
the REVERSE of the LATTICE ENERGY for NaCl ( H5 = – HLattice )
“LATTICE ENERGY” is defined (in Ebbing & Gammon) as the change in energy
that occurs when an ionic solid is separated into isolated ions in the gas phase, e.g.,
MX(s) M+(g) + X–(g); H Lattice
e.g., NaCl(s) Na+(g) + Cl– (g); HLattice = +786 kJ
(Ebbing & Gammon uses the symbol “U” to represent the lattice enthalpy.)
__________________________________________________________________
ASIDE:
Some texts define lattice enthalpy as the energy RELEASED when separate ions come together
to form one mole of an ionic crystalline solid (values are the negative of the Ebbing values).
Depending upon what text you refer to, you will find two different ways to define electron
affinity. In Ebbing & Gammon’s 10th ed., electron affinity is defined as the energy required to
remove an electron from the atom’s negative ion (in its ground state), i.e.,
Cl– ([Ne]3s23p6) Cl ([Ne]3s23p5) + e– ; HEA = +349 kJ
(i.e., electron detachment)
In Ebbing & Gammon’s 9th ed., electron affinity is defined as the energy change during the process
of adding an electron to a neutral atom in the gaseous state to form a negative ion, i.e.,
Cl ([Ne]3s23p5) + e– Cl– ([Ne]3s23p6); HEG = -349 kJ
(i.e., electron-gain enthalpy)
So when you compare the values in Table 8.4, one is the negative of the other.
____________________________________________________________________________________________________
29
NOTES:
So, let’s add up our 5 steps and cancel out any intermediates.
Total of steps 1 5:
1. Sublimation of Na: Na(s) Na(g); H1 = 108 kJ
+ –
+ 2. First Ionization Energy of Na(g): Na(g) Na (g) + e ; H2 = 496 kJ
+ 3. One-half the Bond Enthalpy for Cl2(g): ½Cl2(g) Cl(g); H3 = 120 kJ
+ 4. Electron-gain Enthalpy for Cl(g): Cl(g) + e– –
Cl (g); H4 = –349 kJ
+ 5. Reverse Lattice Enthalpy: Na+(g) + Cl–(g) NaCl(s); H5 = –781 kJ
(Energy is released in this process.)
Therefore: H1 + H2 + H3 + H4 + H5
( Hsubl) + (IE1) + (½ HBD) +( G1 ) + (– HLE)
= – 406 kJ/mol ( Hf {NaCl(s)}
This is a specific example of the use of Hess’ Law known as a
BORN-HABER CYCLE (refer to Figure 9-3 in 10th ed. or 9.2 in 9th ed.).
Magnitude of Lattice Enthalpies

- depends on the charge of the ions and their separation.
- Lattice Enthalpy is dependent upon Coulomb’s law (i.e., electrostatic interaction)
k Q1 Q2
V
r
k is a physical constant, equal to 8.99×109 Jm/C2
Q's are the charges on the ions, and
r is the distance between the ions.
If the charges on the ions are of opposite sign, energy is released (exothermic)
when the two ions are brought together to form an ionic compound. If the
charges on the ions have the same sign, then energy is absorbed (endothermic).
The smaller the value of r, the bigger is V.
Question: Which of the following ionic compounds has the largest lattice energy?
A) CsI
B) NaCl
Charge of Mg and O
C) LiF are 2+ and 2-
D) CsF
E) MgO
30
Lattice Enthalpies in kJ/mol NOTES:
LiF 1046 .... LiI 759
NaF 929 .... NaI 700
KF 826 .... KI 645
MgF2 2961 .... MgI2 2327
MgO 3850 .... BaO 3114
MgS 3406 .... BaS 2832
Due to the electrostatic interactions, lattice enthalpies are LARGER

for short ion separations and/or larger ionic charges.
EXAMPLE:
Determine the lattice enthalpy of magnesium oxide from the following information:
Enthalpy of formation for Mg(g): + 147 kJ/mol MgO(s) —> Mg2+(g) + O2-(g)
st MgO(s) —> Mg(s) + 1/2O2(g) -∆Hƒ˚(MgO(s)) = 601 kJ/mol
1 ionization energy for Mg(g): + 738 kJ/mol Mg(s) —> Mg(g) ∆Hƒ˚(Mg(g)) = 147 kJ/mol
2nd ionization energy for Mg(g): +1451 kJ/mol Mg(g) —> Mg+(g) + e- ∆H˚(IE(1)) = 738 kJ/mol
Mg+(g) =-> Mg2+(g) + e- ∆H˚(IE(2)) = 1451 kJ/mol
Enthalpy of formation for O(g): + 249 kJ/mol 1/2O2(g) —> O(g) 1/2∆H˚(BE) = ∆Hƒ˚(O(g)) = 249 kJ/mol
Electron-gain enthalpy for O(g): – 141 kJ/mol O(g) + e —> O-(g) ∆H˚(EG(1)) = -141 kJ/mol
O-(g) + e- —> O2- (g) ∆H˚(EG(2)) = 917 kJ/mol
–
Electron-gain enthalpy for O (g): + 917 kJ/mol MgO(s) —> Mg2+(g) + O2-(g) ∆H˚(Lattice) = ? kJ/mol
∆H˚(Laatice) = 3963 kJ/mol
Enthalpy of formation for MgO(s): – 601 kJ/mol
PROBLEMS:
1. Compare CaO and BaO. Which one has the more positive lattice enthalpy?
2. Calculate the lattice enthalpy of calcium sulfide from the following information:
enthalpy of formation for Ca(g): + 178 kJ/mol
1st ionization energy for Ca(g): + 590 kJ/mol
nd
2 ionization energy for Ca(g): +1145 kJ/mol
enthalpy of formation for S(g): + 279 kJ/mol
electron-gain enthalpy for S(g): – 200 kJ/mol
electron-gain enthalpy for S–(g): + 532 kJ/mol
enthalpy of formation for CaS(s): – 482 kJ/mol
3. Calculate the lattice enthalpy of calcium bromide.

Here is some information to help you complete this calculation:
enthalpy of formation of CaBr2: – 683 kJ/mole
bond enthalpy of Br2(g): + 112 kJ/mole
electron-gain enthalpy for Br(g): – 325 kJ/mol
4. Place the following compounds in order of increasing Lattice Enthalpies?

A) LiCl, NaCl, BeCl2
B) MgO, MgF2, MgBr2
C) MgCl2, BeO, BeCl2
Answers: 1. CaO since Ca has a smaller radius than Ba.
2. 3006 kJ/mol
3. 2089 kJ/mol
4. a) NaCl<LiCl<BeCl2; b) MgBr2<MgF2<MgO; c) MgCl2<BeCl2<BeO
31
ENTROPY (Refer to Chapter 18) NOTES:
Is there a thermodynamic function that will indicate whether or not a reaction will occur
spontaneously?
Note: By “spontaneously” we mean that the reaction will occur, as
written, on its own with no external intervention.
Systems spontaneously change in such a manner as to decrease their capacity for

change, i.e., approach a state of equilibrium, e.g., gases mixing, solutes dissolving,
ice melting and cards shuffled.
The REVERSE of these processes is NOT spontaneous, i.e., they are non–
spontaneous or irreversible. Non–spontaneous processes require external work to
1. Chemical reactions
make the process occur, e.g., electrolysis of water: H2O(l) H2(g) + ½O2(g) 2. Heat flow from hot to cold
objects, ∆H = 0
3. Micing of 2 gases. ∆H = 0
None of these above processes are forbidden by the 1st Law – energy is still conserved. Expansion of gas into a vauum, ∆H
=0
In some spontaneous processes H is:
Positive, e.g., H2O(s) H2O(l); HRxn = + 6 kJ
NaCl(s) Na+(aq) + Cl–(aq); HRxn = +3.9 kJ
Negative, e.g., 4Fe(s) + 3O2(g) 2Fe2O3(s); HRxn = – 1648 kJ

2H2(g) + O2(g) 2H2O(l); HRxn = –570 kJ
Zero, e.g., mixing of 2 gases or expansion of a gas into a vacuum

Consideration of H alone is not enough. The spontaneous processes are accompanied by
an increase in disorder or randomness in the system, and this leads to the idea of some
other property.
Let’s look at heat flow: HOT COLD. Heat is the product of two terms:
1) an intensity factor, i.e., T
2) a quantity (or capacity) factor i.e., an extensive factor
The second term is known as ENTROPY‡, S
Heat (q) = T S OR S = qRev/T
where S has units of J K OR J mol K– 1
–1 –1
qRev – refers to heat supplied reversibly. Reversibly: processes

(Reversible implies that the system can be restored to the original can be moved in either
state by exactly reversing the change, e.g., melting & freezing) direction
T – refers to the temperature at which the transfer takes place.
Entropy (S) – a STATE function (independent of the path).

a measure of randomness
a thermodynamic quantity that is a measure of how dispersed the energy of a or disorder
system is among the different possible ways that system can contain energy.
measures probability or number of equivalent arrangements of the same energy.
is dependent upon the size of the system, i.e., extensive
‡
The word entropy is derived from the Greek words “en” (in) and “trope” (change, transformation).
32
Two situations: NOTES:
1) Positional – distribution of species in space
e.g., mixing of two gases or the expansion of a gas into a vacuum
2) Thermal – distribution of energy among species, or distribution of

species over energy levels, e.g., heat flow from hot to cold objects
Second Law of Thermodynamics: in any spontaneous process, the

total entropy of the universe must INCREASE, i.e.,
STOTAL = Suniverse = Ssystem + Ssurroundings > 0
So we can have THREE scenarios:

1) Spontaneous processes, Suniv > 0 2. not moving
2) Processes at equilibrium, Suniv = 0
3) Non–spontaneous processes, Suniv < 0
(i.e., spontaneous in the reverse direction)
For any substance entropy rises with temperature. This is due to more atomic/molecular
motions and therefore more ways the system can contain energy. H does not vary
much with temperature, but S does!
When a perfect crystalline substance is at absolute zero (T = 0 K), S = 0.

This is the 3rd Law of Thermodynamics.
Therefore, since we can define a situation where S = 0,
absolute values of S can be determined (see Appendix C), unlike H and U S is measurable
where only changes can be measured.
S values are ALWAYS POSITIVE
S values for stable forms of pure elements at 298K and 1 atm are NOT
ZERO (unlike Hf values of elements).
33
Phase S (J) T NOTES:
Solid 0 0
Solid 59.0 54.4
Liquid 67.2 54.4
Liquid 94.2 90.1
Gas (1 atm) 169.8 90.1
Gas (1 atm) 192.9 200.0
Gas (1 atm) 205.1 298.2
We can define a STANDARD MOLAR ENTROPY, S m
It is important that you realize what the means in terms such as S . It means
that for gases we have a pressure of 1 atm and for solutes we have 1 M
concentrations. Liquids and solids are in their "pure" or "normal" state. NO
mention of temperature – the convention is 25 C
Entropies, unlike enthalpies, are strongly dependent on pressure

(gases) and concentration (solutes).
Typical S m values:
e.g., H2(g) 130.57; F2(g) 202.67; Br2(l) 152.23; I2(s) 116.14 J K–1 mol–1
Factors affecting Sm qualitative approach to predicting S

1. Sm increases with melting and vaporization
S (s) < S (l) < S (g)
e.g., for water 47.5 < 69.95 < 188.7 J K–1 mol–1
Note: S for gases decreases with increasing pressure.
2. Sm increases when a solid or liquid is dissolved in a solvent.
e.g., NaCl(s) vs. NaCl(aq)
72.12 < 115.4 J K–1 mol–1
3. Sm decreases when a gas is dissolved in a solvent.
e.g., CO2(g) vs.. CO2(aq)
214 > 121 J K–1 mol–1
For similar substances in the same physical state, the following factors are useful to know
4. Sm increases with increasing mass (energy levels are more closely spaced as
mass increases).
He(g) vs. Ne(g) vs. Ar(g)
126 < 146 < 155 J K–1 mol–1
5. Sm increases with increasing number of atoms in the molecule (increasing
complexity, numbers of conformations, etc.)
CH4(g) vs. C2H6(g) vs. C3H8(g) vs. n–C4H10(g)
186 < 230 < 270 < 310 J K–1 mol–1
6. Sm increases with increasing molecular freedom or flexibility.
cyclobutane C4H8(g) vs. n–C4H10(g)
265 < 310 J K–1 mol–1
34
QUESTIONS: Which substance in each pair has the higher molar entropy? NOTES:
1. A) CH4(g) OR B) C3H8(g) 3. a) is forced into a
smaller space and
2. A) KCl(aq) OR B) KCl(s) confined
3. A) O2(g, 2 atm, 300 K) OR B) O2(g, 1 atm, 300 K) 4. b) at a higher temp,
more kinetic energy so
4. A) N2(g, 1 atm, 273 K) OR B) N2(g, 1 atm, 450 K) more possibilities for
the distribution of
space
Examples: Predict the SIGN of S
1. liquid is more condensed
1. 2H2(g) + O2(g) 2H2O(l) -
Answer: S is ________ Why? than a gas; 3 mol gases to 2
mol liquid 0 - 3 = - 3
2. 3H2(g) + N2(g) 2NH3(g) Answer: ∆S is - ; going from 4 moles to 2, 2-4 = -2
The calculations are gas subtractions.
3. H2O(l) H2O(g) Answer: ∆S is + ; liquid to gas Gas moles in products - gas moles in reactants = ?
4. CaCO3(s) CaO(s) + CO2(g) Answer: ∆S is + ; 1 - 0 = 1
5. O2(g) O2(aq) Answer: ∆S = -
Additional Examples: Predict whether each of the following processes involves

an increase or a decrease in entropy or whether the outcome is uncertain:
(a) The decomposition of ammonium nitrate (a fertilizer & highly explosive cmpd):
2 NH4NO3(s) 2N2(g) + 4H2O(g) + O2(g)
(b) The conversion of (a key step in the manufacture of sulfuric acid):
2SO2(g) + O2(g) 2SO3(g)
(c) The extraction of sucrose from cane sugar juice: C12H22O11(aq) C12H22O11(s)
(d) The “water gas shift” reaction (involved in the gasification of coal):
CO(g) + H2O(g) CO2(g) + H2(g)
Answers: a) A solid yields a large quantity of gas. Entropy increases.

b) Three moles of gaseous reactants produce two moles of gaseous products. The loss of
one mole of gas indicates a loss of volume available to a smaller number of gas molecules.
This loss reduces the number of possible configurations for the molecules in the system and
the number of accessible microscopic energy levels. Entropy decreases.
(c) The sucrose molecules are reduced in mobility and in the number of forms in which their
energy can be stored when they leave the solution and arrange themselves into a crystalline
state. Entropy decreases.
(d) The entropies of the four gases are likely to be different because their molecular
structures are different. The number of moles of gases is the same on both sides of the
equation, however, so the entropy change is likely to be small if the temperature is constant.
On the basis of just the generalizations listed above, we cannot determine whether entropy
increases or decreases.
35
USING TABULATED S m VALUES TO NOTES:
CALCULATE ENTROPY CHANGES
For any reaction we can write
SRxn = nS m (Products) – nS m (Reactants)
and we can use data from tables of S m to calculate S rxn.
Refer to data in Appendix C.
Remember: S values for elements in their most stable forms at 298 K, 1 atm are NOT
ZERO (unlike H f) and are always positive. BUT note that S , aq) = 0, by definition.
__________________________________________________________________
Problems:
1. Hydrazine and hydrogen peroxide are used as rocket fuel. Using tabulated data, calculate
S for the reaction: N2H4(l) + 2H2O2(l) N2(g) + 4H2O(g), H = –642 kJ mol–1
S Rxn =
= +607 J K–1 mol–1
{large and positive as you would have predicted qualitatively}
2. Calculate the entropy changes associated with
(a) the vaporization of 1 mole of liquid water.
(b) the combustion of 1 mole methane.
(a) Chemical equation is:

S Rxn =
= 118.81 J K–1 (+ve, as expected)
(b) Chemical equation is:

S Rxn =
= –242.76 J K–1 (–ve, as expected)
EXAMPLE TO CONTEMPLATE:
For, 2H2O(l) 2H2(g) + O2(g) we predict S Rxn to be positive
(0 moles gas 3 moles gas)
S Rxn =
=
=
What about the Reverse Reaction?
2H2(g) + O2(g) 2H2O(g), S Rxn = –88.8 J/K … but we know the system goes
Entropy-wise this reaction is not favourable for the system.

What about the surroundings?
36
We need to know SSurroundings (b/c SUniverse = SSurroundings + SSystem > 0) NOTES:
we could get this from SSurroundings = qSurroundings/T
we can figure out the heat given off in the reaction:
Rxn = 2 H f H2O, g) – [2 H f H2, g) + H f 2, g)]
Rxn = = –483.6 kJ
Since System = – Surroundings, then = + 483.6 kJ

Surroundings
SSurroundings = +485.6 kJ/298K = 1620 J/K

SUniverse = SSurroundings + SSystem = –88.8 + 1620 = 1531.2 J/K
So, although the system entropy is BAD, SUniverse is GOOD (follows 2nd Law).
____________________________________________________________________________________________________
ENTROPY CHANGES FOR PHASE CHANGES

H Phase Change
Since S = qRev/T, then S Phase Change
TPhase Change
(i.e., S fus = H fus /Tmelt & S vap = H vap /TBoil )
At the melting and boiling points the system is at EQUILIBRIUM.
can therefore calculate S and T from H values for these processes, e.g.,
Tmelt = H fus(J/mol)/ S fus(J/K mol)
this means the mpt’s increase with increasing H fus and with decreasing
S fus, i.e., the greater the intermolecular attractions and the smaller the
increase in disorder, the higher the mpt.
Example: Pentanes H fus (kJ/mol) S fus (J/K mol) Tmelt (K)

n-pentane
CH3CH2CH2CH2CH3 8.4 58.7 143
neo-pentane
CH 3 3.3 12.7 256
|
H 3C – C – CH 3
|
CH 3
EXAMPLE:
With access to data tables ( H f & S values estimate
a) the boiling point of liquid bromine at 1 atm and
b) the melting point of ice at 1 atm.
(a) when bromine boils we have the equilibrium: Br2(l) Br2(g)

Hvaporisation = H f {Br2(g)} – H f {Br2(l)}
= _______
30.9 – ______
0 = 30.9 kJ
Svaporisation = Sm {Br2(g)} - Sm {Br2(l)}

245.4 – ___________
= _______ 152.2 = 93.2 J K–1 = 9.32 10–2 kJ K–1
37
TBoil = qRev/ S = Hvap/ Svap = 30.9 kJ / 9.32e-2 kJ/K MUST BE IN
CELSIUS, MAKE
332 K
TBoil = __________ = 59 C [actual value is 58.78 C] SURE ITS NOT
KELVIN
(b) for melting ice: H2O(s) H2O(l)

TMelt = Hfusion / Sfusion We can use the known
values of ∆H(fusion) and
= 6.01 kJ / 2.20e-2 kJ/K ∆S(fusion), then calculate T
= ________
273 K = ______
0 C [cool!]
To write enthalpy of formation thermochemical equations, one must know the reference forms of the
elements. The reference forms, or the most stable forms (physical state and allotrope) of the elements under
standard thermodynamic conditions, are:
H2(g) He(g)
Li(s) Be(s) B(s) C(s) N2(g) O2(g) F2(g) Ne(g)
Na(s) Mg(s) Al(s) Si(s) P4(s) S8(s) Cl2(g) Ar(g)
K(s) Ca(s) Sc(s) Ti(s) V(s) Cr(s) Mn(s) Fe(s) Co(s) Ni(s) Cu(s) Zn(s) Ga(s) Ge(s) As(s) Se(s) Br2(l) Kr(g)
Rb(s) Sr(s) Y(s) Zr(s) Nb(s) Mo(s) Tc(s) Ru(s) Rh(s) Pd(s) Ag(s) Cd(s) In(s) Sn(s) Sb(s) Te(s) I2(s) Xe(g)
Cs(s) Ba(s) La(s) Hf(s) Ta(s) W(s) Re(s) Os(s) Ir(s) Pt(s) Au(s) Hg(l) Tl(s) Pb(s) Bi(s) Po(s) At2(s) Rn(g)
Note the following reference forms: Carbon - C(s, graphite); Phosphorus - P4(s, white); Sulfur - S8(s, rhombic)
Clicker Questions
Qu#1: Which of the following rxns has H Rxn equal to the bond enthalpy of the bond
that is broken?
A. HCl (g) H +(aq) + Cl –(aq)
B. HCl (g) H +(g) + Cl –(g) Has to be neutral atoms, not charged species
C. HCl (g) H (g) + Cl (g)
Qu#2: Given the following average bond energies: 432 (H–H); 154 (F–F); 565 (H–F) kJ/mol
Estimate H for: H2(g) + F2(g) 2HF(g).
A) −21 kJ
∆H = (H-H) + (F-F) - 2(HF)
B) +21 kJ = 432 + 154 - 2(564)
= -544 kJ
C) +544 kJ
D) –544 kJ
E) +1151 kJ
38
Qu#3: Which molecule has the lowest nitrogen-nitrogen bond energy ?
A) N2H4 H2 - N - N - H2
B) N2F2 F-N=N-F
C) N2 N2 has a triple bond
D) All of the bonds have the same bond energy since they all involve two nitrogens.
Qu#4: Consider the reaction: 2HCl(g) + 185 kJ H2(g) + Cl2(g)

Which of the following is true?
Extra energy had to be added for this chemical equation to have worked
A) The chemical bonds in the products are weaker than those in the reactants.
B) If thermally isolated, the reaction mixture will get cooler as the reaction proceeds. Yes, cause it’s
endothermic
C) The HCl(g) has a negative heat of formation. Endothermic
D) The reaction is endothermic.
a) ∆H˚(Rxn) = 2(H-Cl) - (H-H) - (Cl-Cl)
E) All of these are true. = 2 (H-Cl) > - (H-H) - (Cl-Cl)
=+
Qu#5: Which of the following processes would be expected to have the SMALLEST increase
in S°rxn per mole of benzene?
A) C6H6(s) C6H6(l) Solid —> Liquid ; numbers are close
B) C6H6(s) C6H6(g) Solid —> Gas ; bigger jump
C) C6H6(l) + Br2(l) C6H5Br(l) + HBr(g)

Gas #s are really big
9
D) C6H6(l) + O2(g) 6CO(g) + 3H2O(g)
2
15
E) C6H6(l) + O2(g) 6CO2(g) + 3H2O(g)
2
39
THERMO - PART 4
SPONTANEITY and GIBBS FREE ENERGY
NOTES:
Spontaneous processes tend to minimize energy and maximize disorder.
Some processes are "Enthalpy Driven" with S = 0
(e.g., a ball rolling downhill)
Some processes are "Entropy Driven" with H = 0
(e.g., two inert gases mixing).
Therefore, for a chemical reaction:

If HRxn is negative and SRxn is positive, then the rxn will be spontaneous
(in the forward direction) as both enthalpy and entropy favour the reaction.
If HRxn is positive and SRxn is negative, then the rxn will be non-
spontaneous as both enthalpy and entropy disfavour the reaction (the
reverse reaction will be spontaneous and occur instead).
What about the cases where

(a) Hrxn and Srxn are both positive, OR
(b) Hrxn and Srxn are both negative
How do we decide if a reaction is “spontaneous” or not?
This balance between energy and entropy can be handled by a new term, (Gibbs)
FREE ENERGY (G), and it gets us away from having to worry about Ssurroundings
and hence Suniverse
Derivation:
We know that: Suniverse = Ssurroundings + Ssystem (1)
We also know that at constant T: Ssurroundings = qsurroundings/T = - qsystem /T
If P is also constant, then Ssurroundings = - qsystem,P / T = - system / T (2)

(This is a key relationship!)
Therefore, substituting (2) into equation (1):
Suniverse = _______________
-∆H(sys) / T + Ssystem
Multiply both sides by –T:
–T Suniverse = Hsystem – T Ssystem
**** We define –T Suniverse G= H – T S

where G is called “Free Energy” ****
40
Significance of the Sign of G NOTES:
A reaction at constant temperature and pressure proceeds spontaneously to

minimize its free energy, i.e.,
SPONTANEOUS
If Grxn is NEGATIVE, the rxn is _____________________________.
(i.e., rxn proceeds in the forward direction from reactants to products).
AT EQUILIBRIUM
If Grxn is ZERO, the rxn is _______________________________.
If Grxn is POSITIVE, the rxn is NOT __________________________,

SPONTANEOUS
but will be spontaneous in the reverse direction.
From here on we will use G which includes both enthalpy and entropy. For a reaction to
proceed spontaneously, G must be negative. (Recall that the 2nd Law of Thermodynamics
says that for a spontaneous process, S > 0.) This means that the direction of spontaneous
change it toward lower free energy (i.e., free energy minimization).
The equation G = H – T S can have 4 possibilities:

H Enthalpy driven i.e., GOOD
Endothermic (+) Exothermic (–)
Entropy driven i.e., GOOD
Reaction ALWAYS
Reaction spontaneous
Increasing (+) spontaneous
at HIGH enough T.
(as written)
S
Reaction NEVER
Reaction spontaneous
Decreasing (–) spontaneous
at LOW enough T.
(as written)
To find “High T” or “Low T” values, use T = H/ S (when G=0)

41
Some examples NOTES:
For each example, state when, if ever, the reaction will be spontaneous:
Example 1: H2 (g) + Br2 (l) 2HBr(g); H = –73 kJ & S = +114 J/K
exothermic, and increasing entropy

ALWAYS SPONTANEOUS (i.e., L —> R)
Example 2: NH3 (g) + HCl(g) NH4 Cl(s); H = –176 kJ & S = –285 J/K
exothermic, decreasing entropy

SPONTANEOUS at low T (i.e., T < 618K)
Example 3: NH4 Cl(s) NH3 (g) + HCl(g); H = +176 kJ & S = +285 J/K
endothermic, increasing entropy

SPONTANEOUS at high T (i.e., T > 618K)
Example 4: 3O2 (g) 2O3 (g); H = +285 kJ & S = –137 J/K
endothermic, and decreasing entropy

NEVER SPONTANEOUS
For the examples above, we can plot graphs of G vs. temperature:
So, for some reactions you might need to check out the possible competing H and
S requirements (i.e., is the reaction enthalpy or entropy driven).
42
Clicker Question#1: For the vaporization of a liquid at a given pressure NOTES:
A) G is positive at all temps. ∆H is positive, ∆S is positive therefore, it’s temperature dependent
B) G is negative at all temps. needs heat in order to be spontaneous
C) G is pos. at low T’s but neg. at high T’s.
D) G is neg. at low T’s but pos. at high T’s.
Clicker Question#2: If a reaction is endothermic & non-spontaneous at 25°C, then it

A) can never be spontaneous.
∆H is +
B) can become spontaneous by adding a catalyst. ∆G is + at 25˚C
C) may be spontaneous at higher temperature. ∆S could be + or -
D) is exothermic & spontaneous at high temps.
E) may be spontaneous at lower temperature.
Clicker Question#3: (Based on 18.27 in text.)

Hypothetical elements A(g) and B(g) are introduced into a container & allowed to
react according to: A(g) + 2B(g) AB2 (g). What is true about H?
A) The value is negative. Consider bond enthalpies:
B) The value is positive. ∆H(Rxn) = 0 + 2(0) - 2(BE for A-B)
C) The value is zero. = neg
Standard Molar Free Energies of Formation, G f
Definition: G f is the G for the reaction in which 1 MOLE of a substance in its

standard state is FORMED from its ELEMENTS in their standard states.
G m,f of any pure element (in its standard state) = 0 (just like __________)
∆H˚(m,f)
Refer to Appendix C for G f values.
G m,f is a measure of stability with respect to decomposition of a compound into

its elements under standard conditions.
If G m,f is negative at a particular temperature, the elements that make up
the compound form the compound spontaneously (i.e., the compound is
MORE stable than the elements/product(s) is/are favoured).
If G m,f is positive at a particular temperature, the compound decomposes
spontaneously into its elements (i.e., the compound is LESS stable than the
elements/reactant(s) is/are favoured).
Remember what “standard states” means:

pure liquid; pure solid (most stable form at 1 atm and specified T)
gases (1 atm; at a specified T)
solutes (1M concentration; at a specified T)
43
Question 1: The std. free energy of formation ( G f) for CS2 (g) is +66.85 kJ/mol. NOTES:
What does this say about the molecule CS 2 (g)?
Eqn: C(s) + 1/4 S8(s) —> CS2(g)
∆G˚ƒ [CS2(g)] = +66.85 kJ
Question 2: The standard free energy of formation of benzene is positive. Benzene

is a common, stable organic molecule. Is there a conflict between these facts?
G is a STATE FUNCTION (independent of path)

We can get G rxn EITHER from:
a) Tables of G m,f data (at a specific T, e.g., 25 C)
G – ONLY @ SPECIFIED TEMP
i.e., Use: Rxn = n G m,f (Products) n G m,f (Reactants)
NOTE: This equation can ONLY be used for 25 C when

using G f values given for 25 C.
OR
b) H f and S m data (at any temperature).
i.e., For ANY T we use: G Rxn = ∆H˚(Rxn) - T∆S˚(Rxn)
This equation assumes that both H and S are independent of temperature

(OK for gen. chem., but note that these values do vary with T but not significantly)
Example of calculating G Rxn from H Rxn and S Rxn values

Calculate the standard free energy change for the formation of methane at 298 K
given H f and S m for reactants and products.
Equation: C(s) + 2H2 (g) CH4 (g)
Find H Rxn :
H Rxn =
H Rxn =
Find S Rxn :
S Rxn =
S Rxn =
44
Find G Rxn : NOTES:
G Rxn = H Rxn -T S Rxn
G Rxn =
G Rxn = G f = - 50.7 kJ
Reaction goes at 298 K
Note: At 1000K,
G Rxn = –74.8 kJ – {1000 K × –80.8 J/K × 1 kJ/ 1000 J}
G Rxn = G f = + 6 kJ
Reaction is entropically unfavoured at high T.
Standard Molar Free Energies of Formation

of Aqueous Ions G f (aq)
Recall that for H f of aqueous ions, it was not possible to separate the cation and
anion contributions. We got around this by defining H f (H+, aq) = _____.
0
Similarly, S m (H+, aq) = _____

0 and G m,f (H+, aq) = ____.
0
Concentration and Free Energy

G Rxncan be obtained from:
a) G f values (e.g., at 25 C) & G Rxn = n G m,f (Products ) - n G m,f (Reactants )
b) H f and S m values (at any temperature) and G Rxn = H rxn – T S rxn
We have a problem however. We rarely have standard conditions (1 atm, 1M). These
conditions are unusual and difficult to set up (except for changes of state at 1 atm or 1
M). Much more useful if we have an expression that we can use with any
concentrations. The value of G (not G ) is much more useful and is easily obtained.
REVIEW QUESTION: Complete the following on your own.

For any reactions, Reactants Products, the sign of G Rxn tells us if we are going
forward, backward or at equilibrium.
GRxn Reaction? ( , or )
negative
zero
positive
Hence GRxn must depend on concentrations of reactants and products.

You already know this!
45
Review of REACTION QUOTIENT, Q (material from CHEM*1040) NOTES:
Remember, for a reaction with any concentration or pressure values:
aA + bB cC + dD
Q C = [C]^c [D]^d / [A]^a [B]^b QP = PC^c x PD^d / PA^a x PD^d
This expression contains ANY values, not just those at equilibrium.

Units: Must be molarity for sol’ns and atm (or bar) for gases; relates to std. states
Note: Pure solids and liquids activity 1 within these expressions.
EQUILIBRIUM
If Q = K, then we are at ________________________.
If Q < K, the reaction wants to go Left —> Right, until Q = K (at equilibrium).
i.e., This means that the top portion of the ratio is too small and the bottom portion
Text
is too big. To get Q to equal K, the reaction must make more C and D while using
up A and B. We would say the reaction is spontaneous.
If Q > K, the top of the ratio has values that are too large and the bottom has values
that are too small. We must drive the reaction backwards to use up C and D, and
make more A and B.
i.e., if Q > K, the reaction goes Left <— Right until Q = K.
This reaction is non-spontaneous as written, but spontaneous in the reverse.
How are Grxn and Q/K related?

We can write: G rxn = RT ln(Q/K) = 2.303 RT log 10 (Q/K)
Q/K ln(Q/K) Grxn Direction Spontaneity?
<1 negative negative L R spontaneous rxn
>1 + + L <— R NON-SPONT.
=1 0 0 L<—>R @ EQUIL.
Spontaneous reactions ALWAYS proceed so as to move TOWARDS

a state of EQUILIBRIUM i.e., Q K i.e., Q/K 1
Thus Grxn (via the value of Q) depends on concentrations
(or partial pressures) of the reactants & products.
We need to think carefully about what we mean by Grxn and Gºrxn .
46
Using logarithm rules (i.e., division within a logarithm is the same as subtracting the NOTES:
logarithm of the top from the bottom):
G rxn = RT ln(Q/K) = RT lnQ – RT lnK

which gives us:
G rxn = Gºrxn + RT lnQ
G rxn is the "standard conditions value" which represents the equilibrium state
(i.e., equilibrium values in either units of atm or moles/L).
RT lnQ term is a "correction factor" to account for non-equilibrium conditions.
Grxn reflects the DIRECTION of a reaction under a particular set of conditions
(concentrations or pressures). As reactants are consumed, Grxn will change
and eventually reach 0 when equilibrium is achieved.
DISTANCE FROM EQUIL.
Grxn is then a quantitative expression of ____________________________.
*******************************************************************
Example: Reaction: N2 (g) + 3H2 (g) 2NH3 (g)
At 298K,the partial pressures in a reaction mixture are PN2 = 0.25 atm, PH2 = 0.55
atm and PNH3 = 0.95 atm. Determine Grxn .
Problem Solving Strategy:

Step 1: Determine the value of G rxn using tables of G m,f data and
G Rxn = n G m,f (Products) - n G m,f (Reactants).
Step 2: Determine Q based on the conditions given in the question.
Step 3: Solve for Grxn .
Step 1: G Rxn = n G f (Prods) - n G f (Reacts) =

G Rxn = -33.28 kJ
Step 2: Q = [Prod]/[Reactants] =
Q = 21.7
Step 3: Grxn = G rxn + RT ln Q

Grxn = -25.7 kJ
Grxn is negative. Therefore, the reaction is __________________ in the forward

direction. An increase in NH3 (g) will continue until Q becomes equal to K (the
equilibrium constant) and hence Grxn will become zero (i.e., at equilibrium).
47
To see the relationship between Q and Grxn review the following set of NOTES:
experiments where the partial pressures for the reactants and products are measured
for the following reaction: N2 (g) + 3H2 (g) 2NH3 (g) where
2 3
Grxn = -33.28 kJ + RT ln {PNH3 / PN2 × PH2 }
Note: The equilibrium constant, K, for this reaction at 298K is 6.8×10 5 .
Expt. PN2 PH2 PNH3 Q RT lnQ Grxn

A 1 1 0 0 - -
-6
B 1 1 0.001 1×10 -34.24 -67.52
-2
C 1 1 0.1 1×10 -11.64 -44.92
D 1 1 1 1 0 -33.28
4
E 1 1 100 1×10 +22.83 -10.45
5
F 1 1 825 6.8×10 (=K) +33.28 0.0
5
G 1.47 0.01 1 6.8×10 (=K) +33.28 0.0
5
H 0.01 0.1 2.61 6.8×10 (=K) +33.28 0.0
7
I 0.01 0.1 26.1 6.8×10 +44.77 +11.49
J 0.01 0.001 100 1×1012 +68.48 +35.2
K 0 1 1 + +
*******************************************************************
We need to think carefully about what we mean by Grxn and G rxn
Recall our STANDARD CONDITIONS:

– gases: 1 atm
– solutes: 1 mol / L
– pure solids or liquids: most stable form at 1 atm and specified temperature. USUALLY 25˚C
So, under STANDARD CONDITIONS,

G= G , S= S , H= H
Recall: Grxn = RT ln(Q/K) = RT lnQ – RT lnK,

Under STANDARD CONDITIONS we are NOT AT EQUILIBRIUM therefore,
0
Q = 1, ln Q = _______, ∆G˚ &
G = _______
G = –RT lnK = –2.303RT logK

OR
K = e– G /RT
= 10 – G /2.303RT
48
Every rxn has a definite G associated with a definite K at a particular temp. NOTES:
NEGATIVE
For K >1, ln K is positive and G is ____________________ K has no units cause its
( Products are favoured) thermodynamic
+
For K <1, ln K is negative and G is ____________________
( Reactants are favoured.)
For example: O2 (g) O2 (aq), G = +16.4 kJ/mol Not spontaneous, reactants are favoured
Keq = e ^(-∆G˚ (J/mol) /RT)

e^(-16.4 kJ/mol x 1000 J/kJ / 8.314 J/molK x 298 K)
= 1.33 × 10–3
With G being positive, does this mean that O 2 (g) will not dissolve in water?
G is positive which indicates that the reactant is favoured over the product
but under what conditions?
UNITS and K eq
K eq must be dimensionless (i.e., to be able to take the log of it) and its numerical
value is based on the set of units that make Q = 1 (i.e., std. conditions of 1 M and 1
atm). Each value within the K expression is referenced to the standard state. For
example, (0.89 atm)/(1.0 atm), or (1.4 M)/(1.0 M), and the units cancel!
If we have both solution(s) and gas(es) within a chemical equation, then the solute
concentration is compared to 1M and the partial pressure(s) of the gas(es) is compared
to 1 atm (1 bar), resulting in no units for K.
Note: We ARE allowed to mix concentration and pressure units within the same K
expression. This just produces a different K value than the one arrived at if only
concentration units were used (i.e., KC) or all partial pressures were used (i.e., KP ).
Kc - uses molar conc. compared to 1M

Kp - partial pressure (atm) compared to 1 atm
Keq - generic equilibrium constant
Ka - dissociation of a weak acid into its ions
Kb - dissociaition of a weak base into its ions
Kw - dissociation of water into its ions
Ksp - dissociaition of a salt into ions
Problem 1: Ammonium nitrate dissolves spontaneously and endothermically in

water. What does this tell you (allow you to deduce) about the size and sign of S
for the solution process?
Answer: If the reaction is spontaneous, -
G is __________.
The reaction is endothermic, therefore H is __________.
+
Therefore, +
S must be _________________.
49
Problem 2: NOTES:
The equilibrium constant for the reaction:
NH3 (g) + H2 O(l) NH4 +(aq) + OH– (aq), is 1.75 × 10-5 at 25 C.
a) Calculate G rxn at 25 C
b) Will NH3 (g) react with water when both [NH4 +] and [OH– ] = 1.0×10-6 M
and [NH3 ] = 0.050M?
Ans: a) +27.1 kJ/mol

c) NH3 will react with H2 O
Problem 3:
The equilibrium constant for HCOOH(aq) + H2 O(l) HCOO – (aq) + H3 O+(aq) is
1.8×10–4 at 25 C. Will formic acid spontaneously dissociated when [HCOOH] =
0.050M and [HCOO – ] = [H3 O+] = 2.0×10 –3 M?
Ans: Yes b/c G = -2.0 kJ/mol
Ka = 1.8e-4 Use relationship:
∆G = RT lnQ/K
K at 25˚C is given, need to find Q = -2.0 kJ/mol
Q = (2.0e-3)^2 / 0.05
= 8e-5 Therefore rxn is spontaneous and acid dissociates
Clicker Question#1: For which of the following reactions is G ° negative?

A) HCl(aq) H+(aq) + Cl−(aq) strong acid, completely dissociates ; big K Consider size of K
since ∆G˚ = - RT lnK
B) AgCl(s) Ag+(aq) + Cl−(aq) hates to dissociate; K is gonna be tiny
C) HCO 3 −(aq) CO3 2– (aq) + H+(aq) bicarbonate is a base, it does not want to do this ; it does not want to dissociate
D) All.
E) None.
Clicker Question#2: A liquid is vapourised at its normal boiling point at constant P.

What is true about G ?
A) The value is negative. Temperature for phase change, it is at equilibrium
Liquid <—> Gas @ Tboil
B) The value is positive.
Therefore Q = K
C) The value is zero. and ∆G = RTln(Q/K) = 0
Clicker Question#3: A liquid is vapourised at its normal boiling point at constant P.

What is true about G °?
A) The value is negative.
B) The value is positive. Bpt: Liquid <—> Gas @Tboil ; K = Pgas
Normal: Vapour pressure = 1 atm
C) The value is zero. Therefore k = 1 and ∆G˚ = - RTlnK = 0
50
Temperature & Spontaneity NOTES:
To an approximation, Hrxn and Srxn do NOT vary significantly with temperature.
[H and S do change, but H and S stay almost constant].
So we can write: G rxn (@ T K) = H rxn (at 298 K) – T S rxn (at 298 K)
Also, G rxn (@ T K) = – RT ln K (@ T K)
Remember: K is also dependent on T
Now knowing G rxn at T K, we can then calculate Grxn at T K from the equation:
Grxn (@ T K) = G rxn + RT lnQ
K eq and T
Background for Dry Lab B: Determination of G°, H° & S°
We know, G = –RT ln Keq = H – T S
(–2.303 RT log10 Ka = 2.303 RT pK a = H – T S )
Therefore taking, – RT ln Keq = H – T S & dividing both sides by –RT, we get
lnKeq = –( H RT) + (T S/RT) , or
lnKe q = –( H R) (1/T) + S/R
(y = mx + b)
A plot of lnK (y-axis) vs. 1/T (x axis) will give a straight line of slope – H /R.
For Dry Lab B, instead of using lnKeq = –( H R) (1/T) + S/R,

we use the “log” form of the equation, multiplied by –1, i.e.,
– log Keq = + H 2.303RT) – S/(2.303R) OR
pKa = + H /(2.303RT) – S /(2.303R)
51
For two temperatures T1 and T2 we can write: NOTES:
lnK1 = – H /RT1 + S /R (K1 = Keq at T1 )
lnK2 = – H /RT2 + S /R (K2 = Keq at T2 )
Subtract the first equation from the second:

ln(K2 /K1 ) = (– H /R)[1/T2 – 1/T1 ] = (+ H /R)[1/T1 – 1/T2 ]
ln(K2/K1) = ( H /R)[(T2 – T1)/T1T2] - Van’t Hoff Equation
This can be a very useful equation. For example:

(1) Can get H by knowing two K’s at two different temperatures.
(2) Can get K 2 (different temperature) by know K 1 and H
(3) Can get G at a different temperature by finding K at T if you know, for
example, the value of K at 298 K.
Consider the following two situations:
(A) Reaction is exothermic ( H is negative) and T2 > T1
Then right-hand side of the equation is negative, i.e., ln (K 2 /K1 ) is negative
K1 > K2
i.e., an increase in T shifts equilibrium to the left as reactants are favored.
(B) Reaction is endothermic ( H is positive; rxn wants heat)

Then right-hand side of the equation is positive, i.e., ln (K 2 /K1 ) is positive
K2 > K1
i.e., rxn goes to the right as T increases (favors products).
An increase in temperature shifts a reaction in the direction in which heat is

absorbed. This is accordance with LeChatelier’s Principle (CHEM*1040 topic;
refer to section 14.8).
Problem 1: For the reaction (at 25 C), 2H2 O(l) H3 O+(aq) + OH– (aq), K W = 1.00 × 10-14
and H = +55.8 kJ, calculate the pH of boiling water.
Remember: KW = [H3 O+][OH– ] and KW = [H3 O+]2 since [H3 O+] = [OH– ] in pure water.
pH = - log [H3 O+]
Strategy:
Step 1: Find KW at 100 C
Step 2: Determine [H3 O+] and then pH at 100 C
Two methods can be used:
52
1. a) First find G @ 298K using K @ 298K and G = –RT ln K
b) Determine S using G = H S
c) Find G @ 373K using G = H S , where T = 373K
– G /RT
d) Find K @ 373K using K = e
e) Find pH @ 373K using KW = [H3 O+]2 and pH = - log [H3 O+]
OR
2. a) Use the Van’t Hoff equation and solve for K 2 at T = 373K
b) Find pH @ 373K using KW = [H3 O+]2 and pH = - log [H3 O+]
Answer: pH = 6.02 at 100 C
Problem 2A: At 25 C and 1 atm, H f for I2 (g) = +62.4 kJ and G f for I2 (g) = +19.4 kJ.
(i) Write thermochemical equations corresponding to each of these statements.
(ii) Calculate a value for S at 25 C, 1 atm for the reaction I2 (s) I2 (g)
(iii) If you warm solid I2 (s) in an open crucible, at what temperature will the I2 (s)
spontaneously change to gas.
(iv) Explain clearly why solid I2 has a distinctive smell even though G f for I2 (g) = +19.4 kJ
(i.e., non–spontaneous).
Answers: (i) I2 (s) I2 (g); (ii) S = +144 J K–1 ; (iii) T = 160 C;

–4
(iv) K = 3.98 × 10 = PI2(g) in atm, i.e., a small but
appreciable value – which your nose can detect!
Problem 2B: Now, for the sake of argument, let us suppose that the pressure of I 2 (g) was less than
the vapour pressure value which we have just calculated – say, 1.0 × 10–6 atm and let us calculate
G for the process.
Hint: Q = ?
Answer: Grxn = –14.8 kJ
i.e., the rxn to produce I2 (g) is ______________ (spontaneous/non-spontaneous).
At this point, the reaction is not at equilibrium and will proceed from ________________
(left to right/right to left).
Problem 3: At what temperature will the vapor pressure of water equal 600 Torr?
Assume enthalpy and entropy changes to be independent of temperature.
Question: Expansion of a gas into a vacuum is not only spontaneous but also instantaneous. Is it generally
true that a spontaneous process is also instantaneous? Explain.
Answer: A spontaneous process is one that occurs without any externa l influence. An instantaneous
process is one that occurs almost instantly, that is very rapidly. A spontaneous process may be fast
or slow, so it is not generally true that a spontaneous process is also instantaneous. For example,
an iron nail rusts spontaneously in air but the rusting process is certainly not instantaneous.
53
GIBBS FREE ENERGY & BIOLOGICAL SYSTEMS
Now that you have a better understand of the implications of Gibbs free energy, NOTES:
how is it that human beings exist?
we’re made up of ~100 trillion (1014) cells
cells contain trillions of molecules, containing tens of thousands of atoms
molecules and cells are arranged in structures, i.e., organs, bones, and skin
molecules can synthesized on very short notice, i.e., adrenalin or insulin
Insulin is a highly ordered molecule. It is a protein made up of 51
amino acids.Those amino acids are all connected in exactly the correct
order and folded into exactly the molecular shape needed for its
function in the metabolism of glucose.
(Note: Hydrogen atoms are not shown for simplicity. Carbon atoms
are black, oxygen atoms are red and nitrogen atoms are blue.)
Thermodynamically speaking, we are very, very IMPROBABLE!
So how can we exist??

The answer lies in the coupling of reactions.
Your body extracts Gibbs free energy from the foods we eat. Consider the single nutrient
glucose (also known as dextrose or blood sugar). A large quantity of Gibbs free energy can
be released when glucose is oxidized, i.e.,
C6H12O6(aq) + 6O2(g) → 6CO2(g) + 6H2O(l); ∆G = –2870 kJ
A reaction that releases Gibbs free energy is known as “exergonic”.
When glucose is burned in the presence of air, all the Gibbs free energy is release as thermal
energy. The same quantity of Gibbs free energy is available to the body when glucose is
oxidised, but of course, if this amount of thermal energy were released all at once it would
raise the temperature rapidly and kill many cells. Instead, your body makes use of a large
number of reactions to release Gibbs free energy in small steps and the energy is stored in
small quantities that can be used later.
The most important method by which Gibbs free energy is stored in your body is
through the formation of ATP from ADP. Within a typical human cell, this reaction takes
place 32 times for each molecule of glucose that is oxidized. (In bacterial cells, it takes place
38 times.) The Gibbs free energy released by the exergonic glucose oxidation is then used to
force the endergonic, reactant favoured process, of forming ATP from ADP. The overall
process is
C6H12O6(aq) + 6O2(g) + 32ADP3–(aq) + H2PO4–(aq) →

6CO2(g) + 32ATP4–(aq) + 38H2O(l); ∆G = -1894 kJ
Because the overall reaction releases Gibbs free energy, appreciable quantities of
products can be obtained. A spontaneous (exergonic) reaction is coupled with a
non-spontaneous (endergonic) reaction to “drive” the non-spontaneous reaction to
products.
54
The words “exergonic” and “endergonic” have nearly the same prefixes as “exothermic” NOTES:
and “endothermic”. In both cases “ex” means out and “endo” means into. “Thermic”
indicates that it is thermal energy that is released or taken up. “Ergonic” indicates that it is
Gibbs free energy that is released or used up.
ASIDE: The above equation simplifies the metabolic process by which Gibbs free
energy stored in nutrients is transferred to ATP. The actual process takes place in
three-stages. Stage 1 involves digestion where large molecules are broken down
into smaller ones. Smaller molecules are then converted to acetyl groups attached
to coenzyme A in stage 2. Finally, within the citric acid cycle, the acetyl groups are
oxidized to carbon dioxide and water.
ATP generated from glucose or other nutrients is a convenient and readily available Gibbs
free energy resource. ATP can release Gibbs free energy in packets of 30.5 kJ for each ATP
converted to ADP. This size is convenient for driving many biochemical processes in your
body. When ATP reacts with water (hydrolysis) energy is released:
+ H2O(l) → + H2PO4–(aq)
(ATP)
(ADP)
∆G = –30.5kJ/mol)
Because ATP is high in Gibbs free energy, it is said to be

a high-energy molecule (or ion).
(Aside: Sometimes the bonds in ATP are called “high-energy bonds”, but this a
misnomer because the bonds can be easily broken to form ADP and
release Gibbs free energy.)
ATP and the metabolism of glucose:

When glucose is metabolized by the body the first step involves the attachment of a
phosphate group to the glucose molecule via nucleophilic attack.
+ H2PO4–(aq) + H3O+(aq);
∆G = +13.8 kJ
glucose hexokinase
glucose-6-
phosphate
(Hexokinase catalyzes the reaction between glucose and ATP
where ATP binds to the enzyme as a complex with Mg2+.)
55
How does this work? NOTES:
The reaction is not spontaneous and requires Gibbs free energy but the reaction can
be forced to proceed if coupled to the conversion of ATP to ADP.
ATP4–(aq) + H2O(l) → ADP3–(aq) + H2PO4–(aq) ∆G = –30.5 kJ
2–
glucose(aq) + H2PO4–(aq) → glucose-6-phosphate (aq) + H2O(l) + H (aq); ∆G = +13.8 kJ
+
ATP4–(aq) + glucose(aq) → ADP3–(aq) + H+(aq) + glucose-6- phosphate2–(aq)

∆G = (-30.5 kJ + 13.8) = – 16.7 kJ
The overall negative value of ∆G means the reaction is overall spontaneous and the
products are favoured. Thus the ATP to ADP transformation can force glucose to
react with dihydrogen phosphate. The 16.7 kJ of Gibbs free energy released appears
as heat and is transferred to the surroundings (i.e., you!)
ASIDE: In biochemistry/biological chemistry it is conventional to write these equations in a

shorthand form that indicates that they are coupled. The first stage of glycolysis is thus
represented by
glucose → glucose-6-phosphate2–
ATP ADP
The curved arrow indicates that the ATP to ADP transformation occurs simultaneously with
the glucose to glucose-6-phosphate reaction and that the two are coupled.
Another example:
Proteins are polymers made of amino acids. Consider the formation of the dipeptide (a two
amino-acid unit) alanylglycine from alanine and glycine, which is the first step in the
synthesis of a protein molecule:
Alanine + Glycine → Alanylglycine ∆G = +29 kJ
With the aid of an enzyme, the reaction is coupled to the hydrolysis of ATP as:
ATP + H2O + Alanine + Glycine → ADP + H3PO4 + Alanylglycine
The overall free-energy change, ∆G is (–31 kJ/mol + 29 kJ/mol) = –2 kJ/mol, which means
that the coupled reaction now favours the formation of the product, and an appreciable
amount of alanylglycine will be formed under this condition.
A schematic representation of ATP synthesis and coupled reactions in living systems is
shown below.
56
PROBLEM 1: NOTES:
ATP undergoes hydrolysis with a release of Gibbs free energy. Other organo-
phosphates undergo similar hydrolysis reactions:
creatine phosphate + H2O(l) → creatine + H2PO4–; ∆G = –43.1 kJ
glycerol 3-phosphate + H2O(l) → glycerol + H2PO4–; ∆G = –9.7 kJ
Which of the reactions below are product-favoured?

1. ATP + creatine → creatine phosphate + ADP
2. ATP + glycerol → glycerol 3-phosphate + ADP
Answers:
1. ATP + H2O(l) → ADP + H2PO4–; ∆G = -30.5 kJ
+ creatine + H2PO4– → creatine phosphate + H2O(l) ; ∆G = kJ
ATP + creatine → creatine phosphate + ADP; ∆G = kJ
Products are (favoured or unfavoured)?
2. ATP + H2O(l) → ADP + H2PO4–; ∆G = -30.5 kJ

+ glycerol + H2PO4– → glycerol 3-phosphate + H2O(l) ; ∆G = kJ
ATP + glycerol → glycerol 3-phosphate + ADP; ∆G = kJ
Products are (favoured or unfavoured)?
∆G°′
Recall ∆G° corresponds to 1M solutions (i.e., pH = 1.00).
Cells are typically at a pH of ~7 and body temperature is 37°C (310K).
Biochemists/biological chemists use ∆G°′ where the prime symbol (′)

indicates that the value of Gibbs free energy change is for pH = 7 (i.e.,
1×10–7), the same concentration of H3O+(aq) as in a typical cell, i.e.,
e.g., C6H12O6(aq) + 6O2(g) → 6CO2(g) + 6H2O(l)

∆G° = –2167 kJ
and
∆G°′ = –2870 kJ
Note: Actually the values used in this section were really ∆G°′
where T = 37°C, [H+] = 1×10–7 and all other concentrations are at standard.
57
PROBLEM 2: NOTES:
What is the ∆G°′ for the reaction:
glucose(aq) + ATP4–(aq) → glucose 6-phosphate2–(aq) + ADP3–(aq) + H3O+(aq);
∆G° = +24.8 kJ
The ∆G°′ value differs from ∆G° because one of the concentrations (i.e., H3O+) has the non-
standard value of 10–7 M. That is, ∆G°′ is ∆G for conditions such that every concentration is
1M except for the [H3O+]. Therefore, set ∆G = ∆G°′, calculate Q and then ∆G°′. (Note the
temperature would be body temperature, 37°C.)
∆G°′ = ∆G° + RT lnQ where Q adjusts ∆G° to ∆G°′ by taking into account pH = 7
Remember all conc’ns are at std. conditions (e.g., 1M) with the exception of H3O+.
∴∆G°′ = +24.8 kJ + RT lnQ
[glucose 6-phosphate2- ](ADP 3- ][H3O+ ]

Q=
[glu cos e][ATP 4 - ]
(1)(1)(1 × 10 -7 )
Q= = 1 × 10 -7
(1)(1)
∆G°′ = +24.8 kJ + (8.314×10-3 kJ/mol K)(273+37K) ln (1×10–7)

∆G°′ = +24.8 kJ/ – 41.5 kJ = –16.7 kJ
Using LeChatelier’s principle, we predict more driving force towards products when the
concentration of a product is small (e.g., 1×10–7 M versus 1 M). Therefore ∆G°′ would be
more negative than ∆G°.
EXTRA PROBLEMS
1. Is the rxn H2O(l) → H2O(g) spontaneous at 25°C under std. conditions (i.e., P{H2O, g} = 1 atm )?
2. Deduce the equilibrium vapour pressure of water at 298 K.
3. At what temperature will the equilibrium vapour pressure of water be 1 atm?

[The same as asking "at what temperature does water boil at 1 atm?"]
58
4. Using the data available in tables, calculate a value for the solubility of AgCl in moles/liter.
5. For the reaction, 2H2O(l) H3O+(aq) + OH–(aq), Kw = 1.00 × 10–14 at 25°C,

and ∆H° for the process at 25°C is +55.8 kJ. Use these data to deduce the pH of boiling water.
6. At constant T and P, a process at equilibrium is characterised by which set of equations:

a) ∆H = ∆U
b) ∆S = ∆H – ∆nRT
c) ∆G = 0
d) ∆U = ∆H + ∆nRT
e) ∆H = ∆U + ∆nRT
7. Consider your favourite weak acid, acetic acid. HAc(aq) H+(aq) + Ac–(aq)
Calculate a value of Ka for acetic acid using ∆G°f (CH3COO–) = -372.5 kJ/mol and
∆G°f (CH3COOH) = -399.6 kJ/mol.
8. The conversion of one mole of n–butane to iso–butane has ∆H° = –6.90 kJ and ∆S° = –15.4 JK–1
Under standard conditions the reaction is
a) Spontaneous at all temperatures
b) Not spontaneous at any temperature
c) Spontaneous at temperatures > 175°C
d) Spontaneous at temperatures < 175°C
9. ∆Hvap for water at its boiling point is 40.6 kJ mol–1.

∆S (J K–1) for the condensation of 1 mole of H2O(g) to H2O(l) at the boiling temperature is:
a) +109
b) +40600
c) +136
d) –109
e) –40600
f) –136
10. For the evaporation of a mole of CCl4(l), ∆H° = 32.8 kJ and ∆S° = 95.1 JK–1.
The normal boiling point of CCl4(l) is?
59
11. For the gas reaction N2(g) + 3H2(g) 2NH3(g), ∆H° = –92 kJ and ∆S° = –197 JK–1.
a) What is ∆G° for the reaction at 25°C?
b) What is the value of Kp at 25°C
12. Rusting of iron is given by the expression: 4Fe(s) + 3O2(g) 2Fe2O3(s) at 25°C.
Given: ∆H°(Fe2O3, s) = –82.6 kJ S°(Fe2O3, s) = 90 J.K–1
S°(Fe, s) = 27 J.K–1 S°(O2, g) = 205 J.K–1
Calculate the equilibrium constant for this process and comment on the magnitude of your answer.
13. Copper sulfate is found as two hydrates – white and blue:

CuSO4.H2O(s) + 4H2O(g) CuSO4.5H2O(s)
white blue
At 298 K we have the following in the usual units (kJ mol–1 and J K–1 mol–1):
∆H° S°
CuSO4.H2O(s) –1084 150
H2O(g) –242 189
.
CuSO4 5H2O(s) –2278 305
(a) Calculate ∆G° at 15°C (stating clearly any assumptions that you make).
(b) Calculate ∆G for the reaction at 15°C if the water vapor pressure is 0.025 atm at the time.
(c) Now predict which of the two hydrates will be stable at a water vapor pressure of 0.025 atm.
14. At 25°C, Kw for water is 1.0 × 10–14 and ∆H° is 56.9 kJ mol–1. Calculate ∆G° and ∆S° at 25°C.
Calculate the pH of pure water at 4°C.
15. In the presence of acid, cyanide solutions release the poisonous gas HCN.
CN–(aq) + H3O+(aq) HCN(g) + H2O(l); ∆G° = –47.7 kJ
Calculate the lowest pH for which no further reaction occurs when [CN–] = 0.25 M and PHCN = 0.0010 atm.
a) 3.24 b) 6.4 c) 7.8 d) 10.76
16. For Hg(l) Hg(g), ∆H°vap = 61.32 kJ and ∆S°vap = 98.83 J K–1
The equilibrium vapor pressure of liquid mercury at 25°C is:
(a) 0.26 Pa (b) 2.6 × 10–6 kPa (c) 1.4 × 105 atm (d) 0.71 Pa
17. Explain clearly the conditions you would have to have for
(a) ∆GRxn = 0 (b) ∆G°Rxn = 0
60

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Jan 12, 2016

CHEM*1050 – General Chemistry II

Introduction to THERMODYNAMICS NOTES:

Chemical reactions involve a transfer of energy between Thermochemistry:

• “Isolated” – neither mass nor energy may enter or leave.

SURROUNDINGS – the rest of the universe.

• Two ways U can change:

Gives off heat: Exothermic

HEAT (q) Thermal

We can ONLY measure changes in U, not absolute values,

HEAT ENERGY, HEAT TRANSFER and TEMPERATURE

TEMPERATURE – an indication of heat content. During a change in

CHEMICAL REACTIONS AND ENERGY CHANGES Not all combustion

If heat is absorbed (taken in), the reaction is endothermic Melting

We will return to this when looking in detail at chemical reactions.

Heat absorbed FROM

ENTHALPY - is a measure of the difference in heat content, H,

EXOTHERMAL and ENDOTHERMIC PROCESSES

We can measure this heat change through the science of calorimetry.

Hence, q = C × ∆T = n × C × ∆T = mass × s × ∆T s = specific heat

In calorimetry∙ the idea is to ISOLATE the SYSTEM from the SURROUNDINGS.

MM for KF = 58.1 g/mol, therefore # moles of KF added =

1 mole of KF would therefore evolve _______________________ of heat.

Example 2 – Transfer of heat (no chemical reaction):

Total heat produced = warms bomb + warms water bath

COMPRESSION/EXPANSION or P-V WORK (see Figs 6.5 & 6.6)

Compression: work is done ON the system BY the surroundings

UNITS FOR ENERGY

In b), we move from 2 moles of gaseous O3 on the reactant side to 3 moles of O2 on

Work done ____

Heat absorbed BY the system FROM the surroundings (endothermic) +

Heat absorbed FROM

• if w and q are positive, they tend to increase U of the system

INTERNAL ENERGY & ISOTHERMAL EXPANSIONS

• For an isothermal (i.e., ∆T = 0) expansion of an ideal gas, ∆U = 0 because

• Since ∆U = q + w = 0, ∴ w = –q. The system does w joules of PV-work

HEAT CHANGES IN REACTIONS

b) Reactions at Constant Pressure, i.e., open to the atmosphere

Therefore, heat capacities give the rate of change of U and H with T.

∆U and ∆H are STATE functions. (q and w are not!)

∆HEIGHT = HEIGHTFinal – HEIGHTInitial

HOW DO ∆H and ∆U COMPARE FOR A REACTION?

Net result is a shrinking volume (compression), therefore work done by

2. Which of the following is (are) TRUE? cooler

∆H˚ VALUES are given in kJ & a sign is specified (+/-)

A typical ENDOTHERMIC rxn: CaCO3(s) → CaO(s) + CO2(g), ∆H° = +178 kJ

Some Simple Thermochemical Rules & Laws

Question: How much energy is released if we burn 1.00 L CH4(g) at

# moles of CH4(g) at 1.01×105 Pa, 1.00 L and 25°C:

Based on the thermochemical equation given earlier, 1 mole CH4

Hess's Law: Thermochemical equations can be added (or subtracted) to

∆H°fus is always a POSITIVE value; energy has to be added to weaken

i.e., In general, ∆H°Reverse process = –∆H°Forward process

B. Enthalpy of Vaporization, ∆𝑯𝑯°𝒗𝒗𝒗𝒗𝒗𝒗 enthalpy change when we vapourise

What is the name for the reverse process? (condensation)

Heating Curve for Water

boiling point ∆H°vap gas

Time heat supplied

C. Enthalpy of Sublimation, ∆𝑯𝑯°𝒇𝒇𝒇𝒇𝒔𝒔 :

e.g., H2O(s) → H2O(g); ∆𝐻𝐻𝑓𝑓𝑓𝑓𝑠𝑠

H2O(s) → H2O(l); ∆𝐻𝐻𝑓𝑓𝑓𝑓𝑓𝑓

What is the name for the reverse process? (deposition)