Thermochemistry Chapter 6 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Energy is the capacity to do work Radiant energy comes from the sun and is earth’s primary energy source Thermal energy is the energy associated with the random motion of atoms and molecules Chemical energy is the energy stored within the bonds of chemical substances Nuclear energy is the energy stored within the collection of neutrons and protons in the atom Potential energy is the energy available by virtue of an object’s position 6.1

Heat is the transfer of thermal energy between two bodies that are at different temperatures. Energy Changes in Chemical Reactions Temperature is a measure of the thermal energy C 40 0 C greater thermal energy 6.2 Temperature = Thermal Energy

Thermochemistry is the study of heat change in chemical reactions. The system is the specific part of the universe that is of interest in the study. open mass & energyExchange: closed energy isolated nothing 6.2

Exothermic process is any process that gives off heat – transfers thermal energy from the system to the surroundings. Endothermic process is any process in which heat has to be supplied to the system from the surroundings. 2H 2 (g) + O 2 (g) 2H 2 O (l) + energy H 2 O (g) H 2 O (l) + energy energy + 2HgO (s) 2Hg (l) + O 2 (g) 6.2 energy + H 2 O (s) H 2 O (l)

ExothermicEndothermic 6.2

First law of thermodynamics – energy can be converted from one form to another, but cannot be created or destroyed.  E system +  E surroundings = 0 or  E system = -  E surroundings C 3 H 8 + 5O 2 3CO 2 + 4H 2 O + energy Exothermic chemical reaction! 6.3 Chemical energy lost by combustion = Energy gained by the surroundings system surroundings

Enthalpy (H) is used to quantify the heat flow into or out of a system in a process that occurs at constant pressure.  H = H (products) – H (reactants)  H = heat given off or absorbed during a reaction at constant pressure H products < H reactants  H < 0 H products > H reactants  H > 0 6.4

 H = heat given off or absorbed during a reaction AT CONSTANT PRESSURE What’s the big deal about the constant pressure?

Another form of the first law for  E system 6.3  E = q + w  E is the change in internal energy of a system q is the heat exchange between the system and the surroundings w is the work done on (or by) the system w = -P  V when a gas expands against a constant external pressure IF we only deal with a situation at constant pressure, we don’t have to worry about ‘w’… we can just focus on the heat exchange and say that it is equal to the change in the internal energy of the system… the potential energy captured in the bonds of the chemicals involved.

Thermochemical Equations H 2 O (s) H 2 O (l)  H = 6.01 kJ Is  H negative or positive? System absorbs heat Endothermic  H > kJ are absorbed for every 1 mole of ice that melts at 0 0 C and 1 atm. 6.4

Thermochemical Equations CH 4 (g) + 2O 2 (g) CO 2 (g) + 2H 2 O (l)  H = kJ Is  H negative or positive? System gives off heat Exothermic  H < kJ are released for every 1 mole of methane that is combusted at 25 0 C and 1 atm. 6.4

H 2 O (s) H 2 O (l)  H = 6.01 kJ The stoichiometric coefficients always refer to the number of moles of a substance Thermochemical Equations If you reverse a reaction, the sign of  H changes H 2 O (l) H 2 O (s)  H = kJ If you multiply both sides of the equation by a factor n, then  H must change by the same factor n. 2H 2 O (s) 2H 2 O (l)  H = 2 x 6.01 = 12.0 kJ 6.4

H 2 O (s) H 2 O (l)  H = 6.01 kJ The physical states of all reactants and products must be specified in thermochemical equations. Thermochemical Equations 6.4 H 2 O (l) H 2 O (g)  H = 44.0 kJ How much heat is evolved when 266 g of white phosphorus (P 4 ) burn in air? P 4 (s) + 5O 2 (g) P 4 O 10 (s)  H = kJ 266 g P 4 1 mol P g P 4 x 3013 kJ 1 mol P 4 x = 6470 kJ

The specific heat (s) of a substance is the amount of heat (q) required to raise the temperature of one gram of the substance by one degree Celsius. The heat capacity (C) of a substance is the amount of heat (q) required to raise the temperature of a given quantity (m) of the substance by one degree Celsius. C = m x s Heat (q) absorbed or released: q = m x s x  t q = C x  t  t = t final - t initial 6.5

How much heat is given off when an 869 g iron bar cools from 94 0 C to 5 0 C? s of Fe = J/g 0 C  t = t final – t initial = 5 0 C – 94 0 C = C q = ms  t = 869 g x J/g 0 C x –89 0 C= -34,000 J 6.5

aka Constant-Pressure Calorimetry commonly used in chemistry lab No heat enters or leaves! q sys = q water + q cal + q rxn q sys = 0 q rxn = - (q water + q cal ) q water = m x s x  t q cal = C cal x  t 6.5 Reaction at Constant P  H = q rxn Using a Cup Calorimeter

6.5

aka Constant-Volume Calorimetry most often used for foods & fuels No heat enters or leaves! q sys = q water + q bomb + q rxn q sys = 0 q rxn = - (q water + q bomb ) q water = m x s x  t q bomb = C bomb x  t 6.5 Using a Bomb Calorimeter Note: What type of calorimeter did you use to determine the heat content of candle wax and snack foods?

Chemistry in Action: Fuel Values of Foods and Other Substances C 6 H 12 O 6 (s) + 6O 2 (g) 6CO 2 (g) + 6H 2 O (l)  H = kJ/mol 1 cal = J 1 Cal = 1000 cal = 4184 J Substance  H combustion (kJ/g) Apple-2 Beef-8 Beer-1.5 Gasoline-34

Special Note: Sometimes standard conditions are noted for  H (  H θ ) Thermochemical standard conditions are defined as Temperature = 25°C* Pressure = kPa (1 atm) [soln] = 1 M * this is different from STP use with gas laws – where standard temperature is 0°C or 273 K