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Enthalpy and Calorimetry

Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Learn the basics of thermochemical equations, enthalpy changes and standard enthalpy of formation.

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Page 1: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Enthalpy and Calorimetry

Page 2: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Reactions Based on Energy Profiles

1. Endothermic Reaction2. Exothermic Reaction

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Page 3: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Endothermic Reaction

1. Reaction which absorbs or requires an amount of energy to proceed.

2. The total energy of the products are higher than the total energy of the reactants.

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Page 4: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Exothermic Reaction

1. Reaction which releases an amount of energy.

2. The total energy of the products are lower than the total energy of the reactants.

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Page 5: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Enthalpy

• Less familiar property of a system• Defined as

H = enthalpy, P = pressuresys

E = internal energy, V = volumesyswww.reaabuan.com/

blog/Prepared: Kemikal Drills by Rea Abuan 2014

Page 6: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Enthalpy is an example of a state

function

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Drills by Rea Abuan 2014

Page 7: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Prepared: Kemikal Drills by Rea Abuan 2014

So let’s define what is a state function first

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Page 8: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

State Functions

• These are properties of the system that are dependent ONLY on the state of the system. • They are not dependent on the

WAY the system came to be in that given state (pathway)

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Page 9: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

State Functions

• Expressed as capital letterse.g. Enthalpy, internal energy, Gibbs Free Energy, entropy, temperature, pressure, volume

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Page 10: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

State Functions

Enthalpy ΔH, Internal energy ΔE,

Gibbs Free Energy ΔG, Entropy ΔS,

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Page 11: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

State Functions

Temperature (Tf – Ti),

Pressure (Pf – Pi),

Volume (Vf –Vi)

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Page 12: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Think of it this way

You and your friend agreed to meet at a coffee shop near your school after an hour.

You’re both coming from your house.

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Page 13: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Think of it this way

You went directly into the coffee shop after an hour. Your friend

took a detour to her house to pick up something before going to the

coffee shop.

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Page 14: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Think of it this way

Your final destination is the same. Your initial position is the

same as well. Think of state functions that way. Their values are independent of the pathway.

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Page 15: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Prepared: Kemikal Drills by Rea Abuan 2014

So going back to enthalpy

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Page 16: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Enthalpy change, ΔH

• is defined as the quantity of heat transferred to or away from the system during a chemical reaction (physical change)

NOTE: system must have constant pressure and mole.

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Page 17: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Enthalpy change, ΔH

enthalpy of the reaction

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Page 18: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Enthalpy change, ΔH

Type of Reaction Enthalpy Change

EndothermicΔH > 0

(positive)

ExothermicΔH < 0

(negative)

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Page 19: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Take note that these changes occur when P =

constant.

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Page 20: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Prepared: Kemikal Drills by Rea Abuan 2014

Now, remember that we cannot measure heat

directly.

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Page 21: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Experimentally, heat associated with

chemical reactions are measured using

calorimetry

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Page 22: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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So let’s discuss calorimetry.

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Page 23: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Calorimetry

is the science of measuring the change in the temperature of the system when it absorbs or

releases energy as heat.

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Page 24: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Ok, one more time.

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Page 25: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Calorimetry

1. Measures the temperature change of a body (note: you should know its specific heat)

2. The temperature change happens due to either absorption or release of energy from the body.

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Page 26: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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The calorimeter!

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Page 27: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Before we continue, take

note of the requirement for

calorimetry

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Page 28: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Remember? There should be a

contant pressure.

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Page 29: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Constant-Pressure Calorimetry

• used for measuring qp (heat at constant temperature) for solution reactions

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Page 30: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Constant-Pressure Calorimetry

• used for measuring ΔHrxn as well, at constant pressure.

NOTE: ΔHrxn ≠ qp

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Page 31: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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You want to use a cat in chemical

calculation?

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Page 32: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Calorimetry Equations Based on

1. Heat transfer involving pure substances (pure water only)

2. Heat transfer involving mixed system (the whole calorimeter)

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Page 33: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

For Pure Substances

where q = heat absorbed /releasedm=mass (g)c = specific heat capacity (J/g⁰C)ΔT = change in temperature

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Page 34: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

For Mixed System

where q = heat absorbed /releasedC = heat capacity (J/⁰C)ΔT = change in temperature

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Page 35: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Let’s check an example

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Page 36: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

A 3.0 g copper was heated from 20°C to 80°C. How much energy was used to heat Cu? (Specific heat capacity of Cu is 24

J/mol °C)

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Page 37: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Given Values:

Mass = 3.0 gramsTinitial =20⁰C

Tfinal = 80 ⁰C

c = 24 J / mol ⁰C

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Page 38: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Solution:

1. Find the value of ΔTΔT = Tfinal – Tinitial

ΔT = 80 ⁰C – 20⁰C ΔT = 60 ⁰C

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Page 39: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Solution:

2. Solve for qq = mc ΔT q = (3.0 g) (24 J /mol ⁰C) (20⁰C)q =1440 J or 1.44 kJ

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Page 40: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Now, we can calculate ΔH rxn

using qp

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Page 41: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Ahm, where’s the cat? meow

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Page 42: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Just remember that in

calorimetry, no heat flows out of the calorimeter

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Page 43: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Prepared: Kemikal Drills by Rea Abuan 2014

The entire system is adiabatic.qsystem = 0

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Page 44: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Prepared: Kemikal Drills by Rea Abuan 2014

Remember this qcal + qH2O = qrxn

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Page 45: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Writing down each equation

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Page 46: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Writing down each equation

or

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Page 47: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Oh crap, there are 4 equations!

Nosebleed

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Page 48: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Chill down a bit. We’ll go through examples for you.

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Page 49: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

When 5.35 kJ of heat is added to a calorimeter containing 23.00 g of water the temperature rises from 14.00oC to 29.55oC. Calculate the heat capacity of the calorimeter in J/oC. The specific heat of water is

4.184 J/g oC.

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Page 50: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Given Values are..

qrxn = 5.35 kJmass water = 23.0 gTi = 14.00 ⁰ CTf = 29.55 ⁰ Cc water = 4.184 J/g oC

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Page 51: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Solve for the change in temperature

ΔT = Tfinal – Tinitial

ΔT = 29.55 ⁰C – 14.00 ⁰C ΔT = 15.55 ⁰C

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Page 52: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Find qwater

qwater = mc ΔT

qwater = (23.0 g) (4.184 J/g oC) (15.55⁰C)

qwater =1496 J or 1.496 kJ

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Page 53: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Recall this qcal + qH2O = qrxn

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Page 54: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Recall this qcal + qH2O = qrxn

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1.496 kJ 5.35 kJ

Page 55: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Solving for qcal

qcal = qrxn - qH2O

qcal = 5.35 kJ - 1.496 kJ

qcal = 3.854 kJ

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Page 56: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Recall again

where q = heat absorbed /releasedC = heat capacity (J/⁰C)ΔT = change in temperature

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Page 57: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

Calculating the heat capacity

qcal

Rearranging,

C = 3.854 kJ / 15.55 ⁰C C = 0.2478 kJ / ⁰C

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Page 58: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Let’s end here. Check out the exercises on my blog.

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Page 59: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Also, check the tutorial videos of problem solving on my blog.

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Page 60: Thermochemistry [Thermochemical Equations, Enthalpy Change and Standard Enthalpy of Formation]

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Until the next post!

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