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CHEM 1050 - General Chemistry II: Introduction To THERMODYNAMICS
CHEM 1050 - General Chemistry II: Introduction To THERMODYNAMICS
CHEM 1050 - General Chemistry II: Introduction To THERMODYNAMICS
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
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
1
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.
WORK (w)
INTERNAL
ENERGY (U)
Mechanical
Surroundings
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.
Object 1 Object 2
THERMOCHEMISTRY (Chapter 6)
– a subset of thermodynamics
– study of the heat given off or absorbed in a chemical reaction.
3
SIGN CONVENTION FOR HEAT PROCESSES NOTES:
PROCESS SIGN
Heat absorbed BY the system FROM the surroundings (endothermic) +
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
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)
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.
4
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
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
5
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)”.
6
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.
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.
8
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.
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) –
10
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
Final
X
Height
X Initial
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
11
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
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.
12
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.
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
________________ 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.
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?"
n=
PV (1.01× 10 Pa)
=
5
(
1 kPa
1000 Pa)(1 L)
=
RT (8.314 kPa ⋅ L ⋅ K ⋅ mol )(298K)
–1 –1
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.
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.
Temp
(°C) liquid
∆H°fus
0°C melting point
solid
Note: ∆H°sub = ∆H°fus + H°vap ...can do this since enthalpy is a state function, i.e.,
16
– 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
________________ 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.
14
– 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
________________ 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.
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?"
n=
PV (1.01× 10 Pa)
=
5
(
1 kPa
1000 Pa)(1 L)
=
RT (8.314 kPa ⋅ L ⋅ K ⋅ mol )(298K)
–1 –1
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.
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.
Temp
(°C) liquid
∆H°fus
0°C melting point
solid
Note: ∆H°sub = ∆H°fus + H°vap ...can do this since enthalpy is a state function, i.e.,
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).
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.
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?
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.
******************************************************************
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.
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!
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 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
What we have seen is an example of a general rule IF we have complete ∆H°f data:
ANOTHER APPROACH:
2CH3CHO(l) → C2H5OH(l) + CH3COOH(l)
ethanal ethanol ethanoic acid
(acetaldehyde) (acetic acid) Elements
20
For Step 1: ∆H° = sum of –∆H°f for all reactants NOTES:
For Step 2: ∆H° = sum of ∆H°f for all products
Note: Watch to make sure you include the coefficients within the balanced equation
(e.g., 2CH3CHO) to arrive at the correct amount of energy.
When using ∆H°f values – you have two ways to choose from:
1) long way (Hess' law)
2) short way (using ∆H°f directly)
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
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)
22
Example from Nature: The Bombardier Beetle defends itself by "shooting" a hot solution
of benzoquinone at its enemies.
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
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.
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
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
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)]
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
___________________________________________________________________________________________________
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)
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
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.).
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
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
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.
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
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!
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
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
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
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
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.
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 =
=
=
2H2(g) + O2(g) 2H2O(g), S Rxn = –88.8 J/K … but we know the system goes
Rxn = = –483.6 kJ
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.
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
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
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#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
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).
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)
40
Significance of the Sign of G NOTES:
AT EQUILIBRIUM
If Grxn is ZERO, the rxn is _______________________________.
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).
Example 2: NH3 (g) + HCl(g) NH4 Cl(s); H = –176 kJ & S = –285 J/K
Example 3: NH4 Cl(s) NH3 (g) + HCl(g); H = +176 kJ & S = +285 J/K
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.
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.
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
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.
zero
positive
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.
=1 0 0 L<—>R @ EQUIL.
46
Using logarithm rules (i.e., division within a logarithm is the same as subtracting the NOTES:
logarithm of the top from the bottom):
Step 2: Q = [Prod]/[Reactants] =
Q = 21.7
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 }
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
= 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 ).
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
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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].
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 )
(y = mx + b)
A plot of lnK (y-axis) vs. 1/T (x axis) will give a straight line of slope – H /R.
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
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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+]
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).
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.
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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.)
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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)
+ 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+.)
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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
+
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.
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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
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)?
∆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).
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.
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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+.
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 )?
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4. Using the data available in tables, calculate a value for the solubility of AgCl in moles/liter.
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
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?
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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.
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
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