Energy & Chemistry

2H2(g) + O2(g) → 2H2O(g) + heat and light

This can be set up to provide ELECTRIC
ENERGY in a fuel cell.
Oxidation:
2 H2 → 4 H+ + 4 e-
Reduction:
4 e- + O2 + 2 H2O → 4 OH-

H2/O2 Fuel Cell

Energy, page 288
 Energy & Chemistry
ENERGY is the capacity to do work or transfer heat.
HEAT is the form of energy that flows between 2 objects
because of their difference in temperature.
Other forms of energy —
• light
• electrical
• kinetic and potential
• Positive and negative particles
(ions) attract one another.
• Two atoms can bond
• As the particles attract they have a
lower potential energy NaCl — composed of
Na+ and Cl- ions.
 Potential & Kinetic Energy
Kinetic energy —
energy of motion.
rotate
vibrate
translate
© 2006 Brooks/Cole - Thomson
 Internal Energy (E)

• PE + KE = Internal energy (E or U)
• Internal Energy of a chemical system depends on
• number of particles
• type of particles
• temperature

• The higher the T the higher the internal energy

• So, use changes in T (∆T) to monitor changes in
E (∆E).
 Thermodynamics
• Thermodynamics is the science of heat (energy) transfer.

Heat transfers until thermal equilibrium is established.

∆T measures energy transferred.

• SYSTEM
– The object under study
• SURROUNDINGS
– Everything outside the system
 Directionality of Heat Transfer
• Heat always transfer from hotter object to cooler one.
• EXOthermic: heat transfers from SYSTEM to
SURROUNDINGS.

T(system) goes down

T(surr) goes up
 Directionality of Heat Transfer
• Heat always transfers from hotter object to cooler one.
• ENDOthermic: heat transfers from SURROUNDINGS to
the SYSTEM.

T(system) goes up
T (surr) goes down
 Energy & Chemistry
All of thermodynamics depends on the law of
CONSERVATION OF ENERGY.
• The total energy is unchanged in a chemical reaction.
• If PE of products is less than reactants, the difference
must be released as KE.
Energy Change in Chemical Processes
PE
Reactants Potential Energy of system
Kinetic
Energy
dropped. Kinetic energy
increased. Therefore, you often
feel a Temperature increase.
Products
 HEAT CAPACITY
The heat required to raise an object’s T by 1 ˚C.

Which has the larger heat capacity?

 Specific Heat Capacity
How much energy is transferred due to
Temperature difference?
The heat (q) “lost” or “gained” is related to
a) sample mass
b) change in T and
c) specific heat capacity

Specific heat capacity = heat lost or gained by substance (J)

(mass, g) (T change,K)
 Substance Phase cp J g-1 K-1 Cp J mol-1 K-1

Air (typical room conditionsA) gas 1.012 29.19

Aluminium solid 0.897 24.2
Argon gas 0.5203 20.7862
Copper solid 0.385 24.47
Diamond solid 0.5091 6.115
Ethanol liquid 2.44 112
Gold solid 0.1291 25.42
Graphite solid 0.710 8.53
Helium gas 5.1932 20.7862
Hydrogen gas 14.30 28.82
Iron solid 0.450 25.1
Lithium solid 3.58 24.8
Mercury liquid 0.1395 27.98
Nitrogen gas 1.040 29.12
Neon gas 1.0301 20.7862
Oxygen gas 0.918 29.38
Uranium solid 0.116 27.7
gas (100 °C) 2.080 37.47
Water liquid (25 °C) 4.1813 75.327
Aluminum
solid (0 °C) 2.114 38.09
All measurements are at 25 °C unless noted. Notable minimums and maximums are
© 2006 Brooks/Cole - Thomson shown in maroon text.
 Specific Heat Capacity
If 25.0 g of Al cool from 310 oC to 37 oC, how
many joules of heat energy are lost by the Al?
Heat/Energy Transfer
No Change in State

q transferred = (sp. ht.)(mass)(∆T)

 Heat Transfer
• Use heat transfer as a way to find specific heat capacity, Cp
• 55.0 g Fe at 99.8 ˚C
• Drop into 225 g water at 21.0 ˚C
• Water and metal come to 23.1 ˚C
• What is the specific heat capacity of the metal?
Heating/Cooling Curve for Water

Note that T is
constant as ice melts
or water boils
 Chemical Reactivity
But energy transfer also allows us to predict reactivity.
In general, reactions that transfer energy to their
surroundings are product-favored.

So, let us consider heat transfer in chemical processes.

 FIRST LAW OF
THERMODYNAMICS

heat energy transferred

∆E = q + w work done
by the
system
energy
change

Energy is conserved!
 The First Law of Thermodynamics

• Exothermic reactions
generate specific amounts
of heat.
• This is because the
potential energies of the
products are lower than
the potential energies of
the reactants.

© 2006 Brooks/Cole - Thomson

 The First Law of Thermodynamics
• There are two basic ideas of importance for thermodynamic
systems.
1. Chemical systems tend toward a state of minimum potential
energy.

2. Chemical systems tend toward a state of maximum disorder.

• The first law is also known as the Law of Conservation of

Energy.
– Energy is neither created nor destroyed in chemical
reactions and physical changes.

© 2006 Brooks/Cole - Thomson

heat transfer in heat transfer out
(endothermic), +q (exothermic), -q

SYSTEM

∆E = q + w

w transfer in w transfer out

(+w) (-w)
 ENTHALPY
Most chemical reactions occur at constant P, so

Heat transferred at constant P = qp

qp = ∆H where H = enthalpy

and so ∆E = ∆H + w (and w is usually small)

∆H = heat transferred at constant P ≈ ∆E
∆H = change in heat content of the system
∆H = Hfinal - Hinitial
 ENTHALPY

∆H = Hfinal - Hinitial

If Hfinal > Hinitial then ∆H is positive

Process is ENDOTHERMIC

If Hfinal < Hinitial then ∆H is negative

Process is EXOTHERMIC
 USING ENTHALPY
Consider the formation of water
H2(g) + 1/2 O2(g) → H2O(g) + 241.8 kJ

Exothermic reaction — heat is a “product” and ∆H = – 241.8 kJ

 USING ENTHALPY
Making liquid H2O from H2 + O2 involves two exothermic
steps.

H2 + O2 gas H2O vapor Liquid H2O

Making H2O from H2 involves two steps.
H2(g) + 1/2 O2(g) → H2O(g) + 242 kJ
H2O(g) → H2O(l) + 44 kJ
H2(g) + 1/2 O2(g) → H2O(l) + 286 kJ
Example of HESS’S LAW—
If a rxn. is the sum of 2 or more others, the net ∆H is the sum of the
∆H’s of the other rxns.
 Hess’s Law & Energy
Level Diagrams

Forming H2O can occur in a single step

or in a two steps. ∆Htotal is the same no
matter which path is followed.

Active Figure 6.18

 Hess’s Law
• Hess’s Law of Heat Summation, Hrxn = H1 +H2 +H3 + ..., states that
the enthalpy change for a reaction is the same whether it occurs by one step
or by any (hypothetical) series of steps.
– Hess’s Law is true because H is a state function.
• If we know the following Ho’s

1 4 FeO(s)  O 2(g)  2 Fe 2O3(s) H  560 kJ

o

2 2 Fe (s)  O 2(g)  2 FeO(g) H  544 kJ

o

3 4 Fe (s)  3 O 2(g)  2 Fe 2O3(s) H  1648 kJ

o

© 2006 Brooks/Cole - Thomson

 Hess’s Law
• For example, we can calculate the Ho for reaction [1] by properly adding (or
subtracting) the Ho’s for reactions [2] and [3].
• Notice that reaction [1] has FeO and O2 as reactants and Fe2O3 as a product.
– Arrange reactions [2] and [3] so that they also have FeO and O2 as reactants and
Fe2O3 as a product.
• Each reaction can be doubled, tripled, or multiplied by half, etc.
• The Ho values are also doubled, tripled, etc.
• If a reaction is reversed the sign of the Ho is changed.

© 2006 Brooks/Cole - Thomson

 Hess’s Law
• Hess’s Law in a more useful form.
– For any chemical reaction at standard conditions, the standard enthalpy change is the sum
of the standard molar enthalpies of formation of the products (each multiplied by its
coefficient in the balanced chemical equation) minus the corresponding sum for the
reactants.

H 0
rxn   n H 0
f products   n H 0
f reactants
n n

n  stoichiome tric coefficients

© 2006 Brooks/Cole - Thomson

 Hess’s Law

© 2006 Brooks/Cole - Thomson

 Hess’s Law
• Given the following equations and Ho values H o
 kJ 
[1] 2 N 2 g   O 2 g   2 N 2 O  g  164.1
[2] N 2 g  + O 2 g   2 NO  g  180.5
[3] N 2 g  + 2 O 2 g   2 NO 2  g  66.4

calculate Ho for the reaction below.

N 2 O g  + NO 2 g   3 NO g  H o  ?
You do it!

© 2006 Brooks/Cole - Thomson

 Hess’s Law
• Use a little algebra and Hess’s Law to get the appropriate Ho values

© 2006 Brooks/Cole - Thomson

 Some Thermodynamic Terms
• Notice that the energy change in moving from the top to the
bottom is independent of pathway but the work required
may not be!
• Some examples of state functions are:
– T (temperature), P (pressure), V (volume), E (change in
energy), H (change in enthalpy – the transfer of heat),
and S (entropy)
• Examples of non-state functions are:
– n (moles), q (heat), w (work)
∆H along one path = ∆H along another path
• This equation is valid because ∆H is a STATE FUNCTION
• These depend only on the state of the system and not how it got there.
• V, T, P, energy — and your bank account!
• Unlike V, T, and P, one cannot measure absolute H. Can only measure ∆H.
© 2006 Brooks/Cole - Thomson
 Some Thermodynamic Terms
• The properties of a system that depend only on the state of the
system are called state functions.
– State functions are always written using capital letters.
• The value of a state function is independent of pathway.
• An analog to a state function is the energy required to climb a
mountain taking two different paths.
– E1 = energy at the bottom of the mountain
– E1 = mgh1
– E2 = energy at the top of the mountain
– E2 = mgh2
– E = E2-E1 = mgh2 – mgh1 = mg(h)

© 2006 Brooks/Cole - Thomson

 Standard States and Standard Enthalpy Changes
• Thermochemical standard state conditions
– The thermochemical standard T = 298.15 K.
– The thermochemical standard P = 1.0000 atm.
• Be careful not to confuse these values with STP.
• Thermochemical standard states of matter
– For pure substances in their liquid or solid phase the standard state is the pure liquid
or solid.
– For gases the standard state is the gas at 1.00 atm of pressure.
• For gaseous mixtures the partial pressure must be 1.00 atm.
– For aqueous solutions the standard state is 1.00 M concentration.
∆Hfo = standard molar enthalpy of formation
• the enthalpy change when 1 mol of compound is formed from elements under
standard conditions.
See Table 6.2 and Appendix L

© 2006 Brooks/Cole - Thomson

 Enthalpy Values
Depend on how the reaction is written and on phases
of reactants and products
H2(g) + 1/2 O2(g) → H2O(g) ∆H˚ = -242 kJ
2H2(g) + O2(g) → 2H2O(g) ∆H˚ = -484 kJ

H2O(g) → H2(g) + 1/2 O2(g) ∆H˚ = +242 kJ

H2(g) + 1/2 O2(g) → H2O(l) ∆H˚ = -286 kJ
 ∆Hfo, standard molar enthalpy of formation
H2(g) + ½ O2(g) → H2O(g) ∆Hf˚ (H2O, g)= -241.8 kJ/mol
C(s) + ½ O2(g) → CO(g) ∆Hf˚ of CO = - 111 kJ/mol
By definition, ∆Hfo = 0 for elements in their standard states.
Use ∆H˚’s to calculate enthalpy change for
H2O(g) + C(graphite) → H2(g) + CO(g)
 Using Standard Enthalpy Values

In general, when ALL enthalpies of

formation are known,

∆Horxn =  ∆Hfo (products) -  ∆Hfo (reactants)

Remember that ∆ always = final – initial
 Using Standard Enthalpy Values
Calculate the heat of combustion of methanol, i.e., ∆Horxn for
CH3OH(g) + 3/2 O2(g) → CO2(g) + 2 H2O(g)
∆Horxn =  ∆Hfo (prod) -  ∆Hfo (react)