Calorimetry

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Calorimetry

Calorimetry is used to physically measure changes in enthalpy.

Bomb calorimetry

Bomb calorimetry uses a machine called a bomb calorimeter to measure enthalpy changes of combustion.
This process involves burning a sample of a compound in a sealed vessel and measuring the temperature change.
- Often the calorimeter will just determine the temperature change in the vessel and you will have to calculate the enthalpy change of combustion.

Inaccuracy

Bomb calorimetry can be inaccurate due to:
- Heat lost to the surroundings.
- Any incomplete combustion that may take place.
- Loss of some reactant that evaporates before it combusts.

Calculating enthalpy changes

The equation to calculate enthalpy changes from temperature changes is:
- q = m × c × ΔT
  - q is the heat energy.
  - m is the mass of the sample.
  - c is the specific heat capacity.
  - ΔT is the temperature change.
If the pressure is constant, q = Δ_cH

Calculating enthalpy changes

We have calculated q, the energy given off to the surroundings (the enthalpy change).
- The units of q are Joules.
To determine the enthalpy change of combustion, we must convert Joules into the unit of enthalpy change, Joules per mole.
- Calculate the number of moles:
  - Moles = mass ÷ M_r
  - ΔH = $\frac{q}{moles}$

More Calorimetry

Calorimetry is a very useful technique to determine enthalpy changes.

Different types of calorimetry

Calorimetry can also be used to measure other enthalpy changes.
We have considered the combustion reaction that gives off heat.
We can also measure any reaction that can be done in a sealed vessel.
- For example, you can measure the enthalpy change of neutralisation of an acid/base reaction.
- These reactions take place in a solution that can be inside the vessel.

Accurate temperature changes

You might think that the best measurements to record are the initial and final temperatures of your calorimeter.
This is not the case.
- This is because heat is always being lost from the calorimeter so the final and initial temperatures are inaccurate.
Instead, measure the temperature loss after the reaction is complete and extrapolate a line to find the true value.
- This is shown clearly in the image on the next slide.

Accurate temperature changes

Line extrapolation is shown above.

Example Calculations - Calorimetry Experiment

Below are some example calculations based on the calorimetry experiment.

Combustion of cyclohexane

Cyclohexane fuel is burned completely in a calorimeter.
- There are 200 g of water in the calorimeter.
- There are 0.5 moles of cyclohexane burnt.
- The temperature of the water was raised from 298 K to 368 K.

The calculation

The calculation:
- q = mcΔT
- q = 200 g x 4.18 Jg^-1K^-1 × 70 K
- q = 58520 Joules
Enthalpy change of combustion = q ÷ moles
- ΔH = −58520 J ÷ 0.5 moles
  - Note the minus sign added. This is because we know the reaction is exothermic since the water's temperature was increased.
- ΔH = −117040 Jmol^-1
- ΔH = −117.04 kJmol^-1
  - Note the final units of kJmol^-1 as this is more standard.

Neutralisation reaction

Calculate the heat lost/gained during the reaction between H₂SO_4(aq) and NaOH_(aq):
- 20 cm³ of the acid is added to an insulate container.
- 30 cm³ of the base is then added.
- The temperature change is recorded to be 40 K.
  - Assume the density of the solutions to be the same as water, 1 gcm^-3.
  - Assume the specific heat capacity is the same as water's, 4.18 Jg^-1K^-1.

The calculation

Because we have assumed that the density is the same as water, we can calculate the mass of the solution as:
- 1 cm³ = 1 g
- (20 + 30) cm³ = 50 g
  - The heat change:
- q = mcΔT
- q = (50) g x 4.18 Jg^-1K^-1 x 40 K
- q = 8360 Joules
- q = 8.36 kJ

1Physical Chemistry

1.1Atomic Structure

1.1.1Fundamental Particles

1.1.2Isotopes & Mass Number

1.1.3Mass Spectrometry

1.1.4Electron Shells, Sub-Shells & Orbitals

1.1.5Electron Configuration

1.1.6Ionisation Energy

1.1.7Factors Affecting Ionisation Energies

1.1.8Trends of Ionisation

1.1.9Specific Impacts on Ionisation Energies

1.1.10End of Topic Test - Atomic Structure

1.1.11A-A* (AO3/4) - Atomic Structure

1.2Amount of Substance

1.2.1Relative Masses

1.2.2The Mole

1.2.3The Ideal Gas Equation

1.2.4Empirical & Molecular Formulae

1.2.5Balanced Equations

1.2.6Percentage Yield

1.2.7A-A* (AO3/4) - Percentage Yield

1.2.8Atom Economy

1.2.9End of Topic Test - Amount of Substance

1.2.10A-A* (AO3/4) - Substances & Yield

1.3Bonding

1.3.1Ionic Bonding

1.3.2Covalent & Dative Bonding

1.3.3Carbon Structures

1.3.4Metallic Bonding

1.3.5Physical Properties

1.3.6Shapes of Molecules

1.3.7Polarity

1.3.8Intermolecular Forces

1.3.9Intermolecular Forces 2

1.3.10End of Topic Test - Bonding

1.3.11Exam-Style Question - Shape of Molecules

1.3.12A-A* (AO3/4) - Bonding

1.4Energetics

1.4.1Enthalpy Changes

1.4.2Calorimetry

1.4.3Hess' Law

1.4.4Bond Enthalpies

1.4.5End of Topic Test - Energetics

1.5Kinetics

1.5.1Collision Theory

1.5.2Maxwell-Boltzmann Distribution

1.5.3Increasing Rates

1.5.4End of Topic Test - Kinetics

1.6Equilibria

1.6.1Le Chatelier

1.6.2Equilibrium Constants

1.6.3A-A* (AO3/4) - Energetics, Kinetics, Equilibria

1.6.4End of Topic Test - Equilibria

1.7Redox

1.7.1Redox

1.7.2End of Topic Test - Redox

2Physical Chemistry 2 (A2 Only)

2.1Thermodynamics (A2 Only)

2.1.1Born-Haber Cycles (A2 Only)

2.1.2Born-Haber Cycle Calculations (A2 Only)

2.1.3Entropy (A2 Only)

2.1.4Free Energy (A2 Only)

2.1.5End of Topic Test - Thermodynamics

2.1.6A-A* (AO3/4) - Thermodynamics

2.2Rate Equations (A2 Only)

2.2.1Rate Equations (A2 Only)

2.2.2Rate Equations 2 (A2 Only)

2.2.3The Arrhenius Equation (A2 Only)

2.2.4Experimental Methods for Rates (A2 Only)

2.2.5End of Topic Test - Rate Equations

2.2.6Exam-Style Question - Rates

2.2.7A-A* (AO3/4) - Rate Equations

2.3The Equilibrium Constant Kp (A2 Only)

2.3.1Properties of Kp (A2 Only)

2.4Electrochemical Cells (A2 Only)

2.4.1Electrochemical Cells (A2 Only)

2.4.2Electrochemical Series (A2 Only)

2.4.3Commercial Application (A2 Only)

2.4.4End of Topic Test - Kp & Electrochemistry

2.4.5A-A* (AO3/4) - Electrochemical Cells

2.5Acids & Bases (A2 Only)

2.5.1Brønsted-Lowry Acids & Bases (A2 Only)

2.5.2pH (A2 Only)

2.5.3The Ionic Product of Water (A2 Only)

2.5.4Weak Acids & Bases (A2 Only)

2.5.5pH Curves & Titrations (A2 Only)

2.5.6pH Curves & Titrations 2 (A2 Only)

2.5.7Buffer Solutions (A2 Only)

2.5.8End of Topic Test - Acids & Bases

2.5.9Exam-Style Question - Weak Acids

2.5.10A-A* (AO3/4) - Acids & Bases

3Inorganic Chemistry

3.1Periodicity & Trends

3.1.1The Periodic Table

3.1.2Trends in the Periodic Table

3.1.3End of Topic Test - Periodicity & Trends

3.2Group 2

3.2.1Group 2 Chemistry

3.2.2End of Topic Test - Group 2

3.3Group 7

3.3.1Introduction to Halogens

3.3.2Reactions of Halogens

3.3.3Chlorine & Chlorate(I)

3.3.4End of Topic Test - Group 7

3.3.5Exam-Style Question - Group 7

3.3.6A-A* (AO3/4) - Periodicity, Group 2 & 7

4Inorganic Chemistry 2 (A2 Only)

4.1Period 3 (A2 Only)

4.1.1Period 3 Elements & Oxides (A2 Only)

4.1.2Period 3 Oxides (A2 Only)

4.1.3End of Topic Test - Period 3

4.2Transition Metals (A2 Only)

4.2.1General Properties (A2 Only)

4.2.2Substitution Reactions (A2 Only)

4.2.3Shapes of Complex Ions (A2 Only)

4.2.4Colours of Ions (A2 Only)

4.2.5Variable Oxidation States (A2 Only)

4.2.6Titrations (A2 Only)

4.2.7Homogeneous Catalysts (A2 Only)

4.2.8Heterogeneous Catalysts (A2 Only)

4.2.9End of Topic Test - Transition Metals

4.2.10A-A* (AO3/4) - Transition Metals

4.3Reactions of Ions in Aqueous Solutions (A2 Only)

4.3.1Acidity (A2 Only)

4.3.2Identification (A2 Only)

4.3.3End of Topic Test - Reactions of Ions in Solution

5Organic Chemistry 1

5.1Introduction

5.1.1Naming Conventions

5.1.2Mechanism

5.1.3Isomerism

5.1.4End of Topic Test - Introduction to Organic Chem

5.2Alkanes

5.2.1Fractional Distillation

5.2.2Cracking

5.2.3Combustion

5.2.4Chlorination

5.2.5End of Topic Test - Alkanes

5.3Halogenoalkanes

5.3.1Substitution Reactions

5.3.2Elimination Reactions

5.3.3Ozone Depletion

5.3.4End of Topic Test - Halogenoalkanes

5.4Alkenes

5.4.1Introduction to Alkenes

5.4.2Reactions of Alkenes

5.4.3Polymerisation Reactions

5.4.4Properties of Polymers

5.4.5End of Topic Test - Alkenes

5.5Alcohols

5.5.1Production of Alcohols

5.5.2Oxidation of Alcohols

5.5.3Oxidation of Alcohols - 2

5.5.4Elimination Reactions

5.5.5End of Topic Test - Alcohols

5.5.6Exam-Style Question - Alcohols

5.6Organic Analysis

5.6.1Reactions

5.6.2Reactions 2

5.6.3Mass Spectrometry

5.6.4Infrared Spectroscopy

5.6.5End of Topic Test - Organic Analysis

5.7A-A* (AO3/4) - Organic 1

5.7.1A-A* (AO3/4) - Organic 1

6Organic Chemistry 2 (A2 Only)

6.1Optical Isomerism (A2 Only)

6.1.1Optical Isomerism (A2 Only)

6.1.2End of Topic Test - Optical Isomerism

6.2Aldehydes & Ketones (A2 Only)

6.2.1Aldehydes & Ketones (A2 Only)

6.2.2End of Topic Test - Aldehydes & Ketones

6.3Carboxylic Acids & Esters (A2 Only)

6.3.1Acids & Esters (A2 Only)

6.3.2Acylation (A2 Only)

6.3.3End of Topic Test - Carboxylic Acids & Esters

6.4Aromatic Chemistry (A2 Only)

6.4.1Structure & Reactivity (A2 Only)

6.4.2Reactions of Benzene (A2 Only)

6.4.3End of Topic Test - Aromatic Chemistry

6.5Amines (A2 Only)

6.5.1Nature & Preparation of Amines (A2 Only)

6.5.2Basicity & Nucleophilicity (A2 Only)

6.5.3End of Topic Test - Amines

6.6Polymers (A2 Only)

6.6.1Condensation Polymers (A2 Only)

6.6.2Biodegradability (A2 Only)

6.7Biological Organic (A2 Only)

6.7.1Amino Acids (A2 Only)

6.7.2Proteins (A2 Only)

6.7.3DNA (A2 Only)

6.7.4Anti-Cancer Drugs (A2 Only)

6.7.5End of Topic Test - Biological Organic

6.8Organic Synthesis (A2 Only)

6.8.1Organic Synthesis (A2 Only)

6.8.2Examples of Synthetic Routes (A2 Only)

6.8.3End of Topic Test - Polymers & Organic Synthesis

6.9NMR Spectroscopy (A2 Only)

6.9.1Understanding NMR (A2 Only)

6.9.2Carbon-13 NMR (A2 Only)

6.9.3Hydrogen-1 NMR (A2 Only)

6.9.4Hydrogen-1 NMR 2 (A2 Only)

6.9.5End of Topic Test - NMR

6.10Chromatography (A2 Only)

6.10.1Overview of Chromatography (A2 Only)

6.10.2Thin-Layer Chromatography (A2 Only)

6.10.3Column Chromatography (A2 Only)

6.10.4Gas Chromatography (A2 Only)

6.10.5End of Topic Test - Chromatography

6.11A-A* (AO3/4) - Organic 2

6.11.1A-A* (AO3/4) - Organic 2

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