Ib PPT 5 SL PDF

IB CHEMISTRY
Topic 5 Energetics/thermochemistry
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Higher level
5.1 Measuring energy changes
OBJECTIVES
• Heat is a form of energy.

• Temperature is a measure of the average kinetic energy of the particles.
• Total energy is conserved in chemical reactions.
• Chemical reactions that involve transfer of heat between the system and the
surroundings are described as endothermic or exothermic.
• The enthalpy change (∆H) for chemical reactions is indicated in kJ mol-1.
• ∆H values are usually expressed under standard conditions, given by ∆H°,
including standard states.
• Calculation of the heat change when the temperature of a pure substance is
changed using q=mc∆T.
• A calorimetry experiment for an enthalpy of reaction should be covered and
the results evaluated.
Temperature and Heat
Temperature is the average kinetic energy of molecules
(K).
Heat is the amount of energy exchanged due to a

temperature difference between two substances (J).
Enthalpy (H)
Enthalpy (H) – the amount of energy or heat
content of a substance. The energy is stored in
the chemical bonds. It includes kinetic and
potential energy and is not measured directly
but changes are measured (J).
Standard enthalpy change of reaction (ΔH⁰) -
the difference between the enthalpy of the
products and the enthalpy of the reactants at
298K and 1.00 x 105Pa.
Enthalpy
• Change in enthalpy (ΔH) – enthalpy of products less
reactants. It is the heat energy change per mole.
ΔH = HP – HR
• For exothermic reactions the temperature of the

surroundings increases and ΔH is negative, energy is
given out
• For endothermic reactions the temperature of the
surroundings decreases and ΔH is positive, energy is
absorbed
• The higher the enthalpy the less stable the substance

Enthalpy level diagrams
Enthalpy level diagrams
• The energy is measured by temperature. We can

calculate the energy change only. Not the energy
stored in the resultant products or reactants.
Exothermic reactions
Examples include:
1. Combustion reactions
2. Neutralization reactions
In an exothermic reaction products:
• have less stored energy
• are more stable
• have stronger bonds (harder to break)
Heat energy change (Q)
Q = mcΔT
m = mass in g
c = specific heat capacity of the substance JK-1g-1
ΔT = change in temperature in K
Q = Heat energy change
ΔH = Heat energy change per mole
So, ΔH = Q /n
Calorimetry
• A technique used to measure enthalpy change.
Heat absorbed, Q = (m x c x T)liquid

c water = 4.18 JK-1g-1
m water = volume in cm3 1 cm3 = 1g
Styrofoam Calorimeter
Bomb
Calorimeter
Assumptions and sources of error
• That no heat is lost to or gained from the surroundings.
• Significant errors are associated with reactions:
– involving the evolution of gas
– involving combustion where hot gas is used to heat liquid in a
calorimeter.
• Heat rises & T under these conditions are reported to be
less than the literature stipulates.
• Thermometers often have precision uncertainty ± 0.1oC
or greater
Measuring Enthalpy changes graphically
Temperature is constantly changing to return to room
temperature so lines are extrapolated to calculate the
value of ∆T.
Problem 1: 1200 kJ of heat is evolved when 2 moles
of magnesium react completely with 1 mole of
oxygen. How much energy is released if 0.600g of Mg
is burnt?
2Mg(s) + O2(g)  2MgO(s)

So Hc(Mg) = -1200kJmol-1/2 = -600 kJmol-1
n(Mg) = m/M = 0.600g/24.3g/mol = 0.0247mol
H = Q/n
so Q = H x n = -600 kJmol-1 x 0.0247mol = 14.8 kJ
Problem 2: 20.0cm3 of 2M NaOH is added to
30.0cm3 HCl of the same concentration. The
temperature increases by 12.0oC. Determine the
heat released.
Total volume is 50.0cm3, water density is 1.00 g cm-
3 so mass of aqueous solution is 50.0g.
Amount of heat required to heat the water, Q
= mcT
= 50.0 g x 4.18Jg-1ᵒC-1 x 12.0ᵒC
= 2508 J or 2.51 kJ
So, 2.51 kJ is the amount of heat energy evolved in
the reaction:
HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l)
So sodium hydroxide is the limiting reagent.

n(NaOH) = CV = 2M x 0.02dm3 = 0.0400 moles
(so the enthalpy PER MOLE can be determined)
H(NaOH) = Q/n = 2.51kJ/0.04moles = 62.7 kJ/mol
The energy is evolved, exothermic, so
H(NaOH) = -62.7 kJ/mol
Problem 3:
300 mL of 0.2 M aqueous KOH neutralizes 150 mL of aqueous 0.2 M H2SO4.
We go from an average initial temperature of 22.3 oC to a maximum of 29.2
oC. Calculate the molar heat enthalpy of neutralisation of KOH and the
molar heat of enthalpy of the reaction.
2KOH + H2SO4  K2SO4 + 2H2O
Q = mcΔT
= (300 + 150 g)(4.19)(29.2-22.3)
=13009.95 J
n(KOH) = CV = 0.2mol/L(0.300 L) = 0.06 mol
n(H2SO4) = CV = 0.2mol/L(0.150 L) = 0.03 mol
For molar enthalpy of neutralisation of KOH:

ΔH = Q/n = -13.10 kJ/0.06 moles = -217 kJ/mol of KOH
For molar enthalpy of the reaction you need to watch for stoichiometric
ratios. There are 2 moles of KOH so divide by 2:
ΔH = Q/n = -13.10 kJ/0.03 moles = -109 kJ/mol
5.2 Hess's Law
OBJECTIVES
• The enthalpy change for a reaction that is carried out in a series of steps is
equal to the sum of the enthalpy changes for the individual steps.
• Application of Hess’s Law to calculate enthalpy changes.
• Calculation of ∆ reactions using ∆Hf° data.
• Determination of the enthalpy change of a reaction that is the sum of
multiple reactions with known enthalpy changes.
Hess’s Law
• In a chemical reaction the total change in
chemical potential energy (enthalpy change)
must be equal to the energy lost or gained by
the reaction system.
Enthalpy level cycles
Therefore according to Hess’s Law:

ΔH = ΔH1 + ΔH2 + ΔH3
Problem 1:
C + ½O2  CO H = – 110.5 kJ

CO + ½O2  CO2 H = – 283.0 kJ
C + CO + O2  CO + CO2 H = – 393.5 kJ
C + O2  CO2 H = – 393.5 kJ
Standard enthalpy change of formation (ΔH⁰f)
Standard enthalpy change of formation (ΔH⁰f) – is the
enthalpy change that results when one mole of a compound is
formed from its elements at 298K and 1.00 x 105Pa. All
reactants and products are in their standard states.
Eg. C(s) + 2H2(g)  CH4(g)

6C(s) + 3H (g) + ½O (g)  C H OH(s)
2 2 6 5
Using Hess’s Law to determine
enthalpy of formation
Hf = Hf of products – Hf of reactants

Problem 1:
Calcium carbonate reacts with hydrochloric acid according to the
following equation:
CaCO3 (s) + 2HCl (aq)  CaCl2 (aq) + H2O (l) + CO2 (g)
Calculate the enthalpy change for this reaction
Horeaction =  Hoproducts –Horeactants
Solution
HoCaCO3 -1207 Hoproducts =(-796)+(-286)+(-394)
= -1476 kJ/mol
Ho HCl (aq) -167
HoCaCl2 -796
Horeactants =(-1207)+(2)(-167)
Ho H2O (l) -286 = -1541 kJ/mol
Ho CO2 (g) -394 Horeaction = -1476-(-1541) = +75 kJ/mol
Problem 2:
Calculate the enthalpy change for the burning of 11
grams of propane
C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(g)
Horeaction =  Hoproducts –Horeactants
Ho C3H8 -104 Solution

Hoproducts =(3)(-394)+(4)(-242)
Ho O2 (g) 0
= -2150 kJ/mol
Ho H2O
(g)
-242 Horeactants =(-104)+(5)(0)
= -104 kJ/mol
Ho CO2 (g) -394 Horeaction = -2150-(-104) = -2046 kJmol-1
Now 11 grams = 0.25 mole of propane (11 g/44 g mol-1)
(0.25 mol )(-2046 kJ mol-1) = 511.5 kJ
Standard Enthalpy of Combustion (∆H°c)
Standard enthalpy change of combustion (ΔH⁰C) – is the
enthalpy change that results when one mole of a compound
reacts with oxygen at 298K and 1.00 x 105Pa. All reactants and
products are in their standard states.
Eg. C(graphite) + O2(g)  CO2(g)

H (g) + ½O (g)  H O(l)
2 2 2
C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l)

Using Hess’s Law to determine
enthalpy of combustion
Hc = Hc of reactants – Hc of products

Problem 1: Calculate the standard enthalpy of formation of
methane; the standard enthalpies of combustion of carbon,
hydrogen and methane are -394, -286 and -890 kJmol-1 .
C(graphite) + 2H2(g)  CH4(g)
Hc = Hc of reactants – Hc of products

= [ (1 x Hc of C) + (2 x Hc of H2) ] - [ 1 x Hc of CH4]
= 1 x (-394) + 2 x (-286) - 1 x (-890)
= -76 kJmol-1
SUMMARY
Horeaction =  Hoproducts – Horeactants
Horeaction = Hof products – Hof reactants
Horeaction = Hoc reactants – Hoc products

Horeactant = Horeaction / mole ratio
5.3 Bond enthalpies
OBJECTIVES
• Bond-forming releases energy and bond-breaking requires energy.

• Average bond enthalpy is the energy needed to break one mol of a bond in a
gaseous molecule averaged over similar compounds.
• Calculation of the enthalpy changes from known bond enthalpy values and
comparison of these to experimentally measured values.
• Sketching and evaluation of potential energy profiles in determining
whether reactants or products are more stable and if the reaction is
exothermic or endothermic.
• Discussion of the bond strength in ozone relative to oxygen in its importance
to the atmosphere.
Bond enthalpy
• Average bond enthalpy is the amount of energy required
to break one mole of bonds in the gaseous state averaged
across a range of compounds containing that bond.
• Breaking bonds is endothermic

• Making bonds in exothermic
• If the overall reaction is exothermic, the bonds have lost

energy, are more stable, and have higher bond enthalpies
• If the overall reaction is endothermic, the bonds have
gained energy, are less stable, and have lower bond
enthalpies
Using Hess’s Law and bond enthalpies
to determine enthalpy of reaction
H =  bond enthalpies –  bond enthalpies

of reactants of products
ATOMS
SUM OFTHE BOND

ENTHALPIES OF SUM OFTHE
THE REACTANTS BOND
ENTHALPIES OF
THE PRODUCTS
REACTANTS
H
PRODUCTS
Bond Enthalpy Table
The average bond enthalpies are in your data booklet:
Problem 1: Calculate the enthalpy change for the
reaction N2 + 3H2  2NH3
Bonds broken
1 N=N: = 945
3 H-H: 3(435) = 1305
Total = 2250 kJ/mol
Bonds formed
2x3 = 6 N-H: 6 (390) = - 2340 kJ/mol
Net enthalpy change

H = reactants – products
= + 2250 - 2340 = - 90 kJ/mol
Bond enthalpies of ozone
Ozone is decomposed more easily than oxygen.
O2 requires 498kJ/mol to break
O3 requires 364kJ/mol to break
O2(g)  O•(g) + O•(g)
O3(g)  O2(g) + O•(g)

The energy profile shows that ozone molecule is
more stable than the oxygen molecule with an
oxygen radical

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IB CHEMISTRY

• Heat is a form of energy.

Heat is the amount of energy exchanged due to a

• For exothermic reactions the temperature of the

• The higher the enthalpy the less stable the substance

• The energy is measured by temperature. We can

Heat absorbed, Q = (m x c x T)liquid

2Mg(s) + O2(g)  2MgO(s)

So sodium hydroxide is the limiting reagent.

For molar enthalpy of neutralisation of KOH:

Therefore according to Hess’s Law:

C + ½O2  CO H = – 110.5 kJ

Eg. C(s) + 2H2(g)  CH4(g)

Hf = Hf of products – Hf of reactants

Ho C3H8 -104 Solution

Eg. C(graphite) + O2(g)  CO2(g)

C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l)

Hc = Hc of reactants – Hc of products

C(graphite) + 2H2(g)  CH4(g)

Hc = Hc of reactants – Hc of products

Horeaction =  Hoproducts – Horeactants

Horeaction = Hof products – Hof reactants

Horeaction = Hoc reactants – Hoc products

• Bond-forming releases energy and bond-breaking requires energy.

• Breaking bonds is endothermic

• If the overall reaction is exothermic, the bonds have lost

H =  bond enthalpies –  bond enthalpies

SUM OFTHE BOND

Net enthalpy change

O3(g)  O2(g) + O•(g)

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