Thermo Chemistry

THERMOCHEMISTRY
H. Esteban 6/14/2012
Thermochemistry
The branch of Chemistry concerned with heat effects accompanying chemical reactions The study of energy in chemical reactions
Energy and Heat

Energy (U) refers to the capacity to do work
Energy transfer
Work is done when Force acts over a distance a form of energy transfer Heat is the transfer of thermal energy between two bodies that are at different temperatures.
Energy
Potential Energy energy by virtue of position
PE = mgh m = mass (kg) g = gravity constant (m s2) h = height (m)
Kinetic Energy energy of motion

KE = 1/2mv2 m = mass (kg) v = velocity (m s1) v2 = (m2 s2)
units are kg m2 s2 J
units are kg m2 s2 J
EOS
The branch of Chemistry concerned with heat effects accompanying chemical reactions
Heat is transfer of thermal energy
What are involved in the transfer?
H. Esteban
6/14/2012
System and Surrounding
System Surrounding
Open Closed Isolated

Heat and Work

Thermal Energy Kinetic energy associated with random molecular motion. In general proportional to temperature. An intensive property. Heat and Work q and w. Energy changes.
H. Esteban
6/14/2012
Endothermic and Exothermic Process

Exothermic process is any process that gives off heat transfers thermal energy from the system to the surroundings. 2H2 (g) + O2 (g) 2H2O (l) + energy
H2O (g)
H2O (l) + energy
Endothermic process is any process in which heat has to be supplied to the system from the surroundings. energy + 2HgO (s) 2Hg (l) + O2 (g)
energy + H2O (s)

H2O (l)
Internal Energy
Internal Energy (U) is the total energy contained within the system, partly as kinetic energy and partly as potential energy
Kinetic involves three types of molecular motion ...
EOS
H. Esteban
6/14/2012
Internal Energy
Internal Energy (U) is the total energy contained within the system, partly as kinetic energy and partly as potential energy
Potential energy involves intramolecular interactions ...

and intermolecular interactions ... EOS
Heat
Energy transferred between a system and its surroundings as a result of a temperature difference. flows spontaneously from higher T lower T flow ceases at thermal equilibrium
EOS
Heat transfer
H. Esteban
6/14/2012
Units of Heat
Calorie (cal) The quantity of heat required to change the temperature of one gram of water by one degree Celsius. Joule (J) (Named after James Joule) SI unit for heat
1 cal = 4.184 J
H. Esteban
6/14/2012
Heat capacity
The quantity of heat required to change the temperature of a system by one degree.
Molar heat capacity (units J mol-1 oC-1)
System is one mole of substance.
Specific heat, c (J g-1 oC-1)

System is one gram of substance
Heat capacity (J oC-1)

Mass X specific heat.
H. Esteban
6/14/2012
Specific Heat and Heat capacity

How much heat is required to raise the temperature of 7.35 g of water from 21.0 to 98.0C. Assume the specific heat of water is 4.18 J g-1 C-1 throughout this temperature range. How much heat, in kilojoules (kJ), is required to raise the temperature of 237 g of cold water from 4.0 to 37.0 C (body temperature)?
Heat
Conservation of Energy
In interactions between a system and its surroundings the total energy remains constant energy is neither created nor destroyed. qsystem + qsurroundings = 0 qsystem = -qsurroundings
H. Esteban
6/14/2012
Determination of Specific Heat
H. Esteban
6/14/2012
EXAMPLE
When 1.00 kg lead (specific heat = 0.13 J g-1 C-1 ) at 100.0 C is added to a quantity of water at 28.5 C, the final temperature of the leadwater mixture is 35.2C. What is the mass of water present?
H. Esteban
6/14/2012
Heat Reactions and Calorimetry

Chemical energy. Contributes to the internal energy of a system.
Heat of reaction, qrxn. The quantity of heat exchanged between a system and its surroundings when a chemical reaction occurs within the system, at constant temperature.
H. Esteban
6/14/2012
Heat Reaction qrxn
Exothermic
Endothermic
H. Esteban
6/14/2012
Bomb Calorimeter
qrxn = -qcal qcal = qbomb + qwater + qwires+
Define the heat capacity of the calorimeter:
qcal = 3miciT = CT
H. Esteban
6/14/2012
Example
Using Bomb Calorimetry Data to Determine a Heat of Reaction. The combustion of 1.010 g sucrose, in a bomb calorimeter, causes the temperature to rise from 24.92 to 28.33C. The heat capacity of the calorimeter assembly is 4.90 kJ/C.
(a) What is the heat of combustion of sucrose, expressed in kJ/mol C12H22O11 (b) Verify the claim of sugar producers that one teaspoon of sugar (about 4.8 g) contains only 19 Calories. Note that 1 food Calorie is actually 1 kcal, so 19 Calories is 19 kcal.
Example
H. Esteban
6/14/2012
Example
You place 25.0 mL of 2.50 M NaOH in a coffeecup calorimeter at 21.1C and carefully add 25.0 mL of 2.50 M HCl, also at 21.1C. After stirring, the final temperature is 37.8C. Calculate qsoln (in J). (Assume the total volume is the sum of the individual volumes and that the final solution has the same density and specific heat capacity as water: d = 1.00 g/mL and c = 4.18 J/g*K)
H. Esteban
6/14/2012
Example Two solutions, 100.0 mL of 1.00 M AgNO3(aq) and 100.0 ml of 1.00 M NaCl (aq), both initially at 22.4 C, are added to a Styrofoam-cup calorimeter and allowed to react. The temperature rises to 30.2 C. Determine qrxn per mole of AgCl (s) in the reaction.

Thermo Chemistry

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THERMOCHEMISTRY

Energy and Heat

Kinetic Energy energy of motion

System and Surrounding

Open Closed Isolated

Heat and Work

Endothermic and Exothermic Process

H2O (l) + energy

energy + H2O (s)

Kinetic involves three types of molecular motion ...

Potential energy involves intramolecular interactions ...

Specific heat, c (J g-1 oC-1)

Heat capacity (J oC-1)

Specific Heat and Heat capacity

Determination of Specific Heat

Heat Reactions and Calorimetry

Heat Reaction qrxn

Define the heat capacity of the calorimeter:

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