Highlights of last lecture

Exothermic and endothermic processes Energy level diagrams Heat and work

First Law of Thermodynamics Eint = q + w

Slide 22-1

Thermochemistry
So, consider, for now, only the work done on a system by compression or expansion against a pressure, i.e. w = -P V Why the sign? Because compression of a gas (i.e a negative change in volume) means that work has been done on the system

So Eint = q + w = q P V
In words when energy changes in a reaction it typically involves a heat flow and a volume change.
Slide 22-2

Enthalpy
Rearrange

Eint + P V = q H ENTHALPY or HEAT OF REACTION

Notice: under conditions of constant volume, H = Eint

It is the experimentally observed heat change for a chemical reaction under conditions of constant pressure.

Slide 22-3

Enthalpy
Why is this so important?
Many practical chemical reactions are performed under constant pressure, rather than constant volume conditions, for example:

laboratory experiments in open containers biological reactions in living systems atmospheric reactions combustion reactions (except in closed system)

So, if you were to measure the heat change in the reaction, you would be measuring H, not Eint Therefore 1. At constant P, calorimetry gives H 2. Tables of H predict heat change under exptal condns Additional Note: Even for gases, H and E are very close (-> problems)
Slide 22-4

Heat Capacity (C and c)

So the more you have of a substance, the less the temperature will rise for a given input of heat Similarly, different substances will change temperature by a different amount (e.g. copper vs ceramic)

q = const x T
The constant must be mass (or moles) dependent, and be different for different substances

q = m c T q = n C T

m = mass of substance (g) n = amount of substance (mol) c = specific heat capacity (J g-1 K-1) C = molar heat capacity (J mol-1 K-1 )
Slide 22-5

Specific Heat Capacities

Q: How much energy (heat) does it take to heat an Al saucepan (0.2 kg) containing 1L of water from room temp. (20C) to boiling? Assume thermal equilibrium between the pan and water at all times.

Q: Why might radiator antifreeze (ethylene glycol) be a bad idea in summer?

Slide 22-6

Calorimetry
At constant pressure, the coffee-cup calorimeter measures the heat of reaction, H.

thermally insulated usually used for liquids esp. good for heat of dissolution heat capacity of solids aqueous reactions
Slide 22-7

Calorimetry
At constant volume, the bomb calorimeter measures the internal energy change, E

(PV = 0 therefore q = E )
thermally insulated usually used for combustion reactions must know the heat capacity of the calorimeter.

Slide 22-8

Example problem
Q: A manufacturer claims that their dessert has fewer than 50 kJ per serving. The Consumer Affairs Department commissioned you to test the claim. Your experiment: You put one serving of the dessert into a bomb calorimeter (c = 8.15 kJ/K) and burnt it to completion in excess O2. The temperature increased by 4.94C. Is the claim justified?

Slide 22-9

Enthalpy of special reactions

Enthalpy of fusion
e.g melting ice H2O(s) (0oC)

H2O(l) (0oC)

Hfus = + 6 kJ mol-1

Enthalpy of combustion:
e.g. BBQ fuel (butane) C4H10 (g) + 6.5 O2 (g) 4 CO2 (g) + 5 H2O (g) Hcomb = -2877 kJ mol-1

Enthalpy of atomisation: (a thought reaction)

e.g. butane C4H10 (g) 4 C (g) + 10 H (g) Hatom = +5544 kJ mol-1
Slide 22-10

Hatom and bond enthalpies

What determines the size of different heats of reaction? Lets consider atomization (this reaction rarely occurs but it is a transformation that can be applied to any molecule) The energy required to reduce a molecule to its atoms is the energy required to break all the bonds. Wouldnt it be nice if we could just add up individual bond enthalpies?

Slide 22-11

Average bond enthalpies are tabulated

Warning: the actual bond enthalpy in a specific molecule differs from these average values. Slide 22-12

Bond enthalpies and Hatom

The atomisation enthalpy is estimated as the sum of the individual average bond enthalpies: Q: What is Hatom for methanol? H H C H O H
3 x C-H = 1248 1 x C-O = 359 1 x O-H = 464 Hatom = 2071 kJ mol-1
Slide 22-13

Bond enthalpies to estimate Hc

CH4(g) + 2 O2(g) CO2(g) + 2 H2O (g);
4 x CH: 2 x O=O: Total: 1652 996 2648

Ec = ?
All units kJ mol-1

2 x C=O: 4 x OH: Total:

1612 1856 3468

Difference Ec = -820 kJ mol-1

Slide 22-14

Bond enthalpies to estimate Hc

In chemical language:
kJ mol-1

CH4 (g) + 2O2 (g) C (g) + 4 H (g) + 4 O (g) C (g) + 4 H (g) + 4 O (g) CO2 (g) + 2 H2O (g) CH4 (g) + 2O2 (g) CO2 (g) + 2 H2O (g)

H = 2648 H = -3468 Hc = -820

This kind of sum is called HESSS LAW

In words If you add up chemical equations to form a new (overall) equation, then the overall enthalpy is the sum of the enthalpies. Note: Using Eatom to estimate reaction enthalpy is only approximate
Slide 22-15

Hesss Law
In a series of chemical reactions, the total energy gained or lost depends only on the initial and final states, regardless of the number or path of the steps Germain Hess 1802-1850
Slide 22-16

Hesss Law
Hesss Law is important. It allows us to calculate thermodynamic quantities for reactions we havent (or cant) measure.

H (kJ/mol) CO (g) + O2 (g) CO2 (g) NO (g) N2 (g) + O2 (g) CO(g) + NO(g) CO2(g) + N2(g) -283.0 -90.3 -373.3

Reaction in catalytic converter to remove NO and CO

Slide 22-17

Summary
CONCEPTS What enthalpy means Concept of calorimetry, and differences between constant P and constant V calorimetry Chemical basis of Hesss Law Heat capacity CALCULATIONS Heat capacity calculations Work and heat calculations (using First Law) Calorimetry problems (working out H or Eint) Hesss Law calculations Estimating reaction enthalpy from bond energies.
Slide 22-18