1. Reaction Energy and Reaction Kinetics
Chapter 17
Reaction Energy and Reaction Kinetics

2. Sect. 17-1: Thermochemistry
Thermochemistry – the study of the transfers of energy as heat that accompany chemical reactions and physical changes
Calorimeter – device used to measure the energy absorbed or released as heat in a chemical or physical change

3. Temperature – a measure of the average KE of the particles in a sample of matter
Joule (J) – the SI unit of heat and energy; kJ is also commonly used
Heat – energy transferred between samples of matter because of a difference in their temperatures

4. Specific heat – the amount of energy required to raise the temperature of one gram of a substance by one degree Celsius.
Units are typically J/(g x°C) or cal/(g x°C)
q = Cp x m x ΔT, where q is heat, Cp is specific heat, m is mass, & ΔT is change in temperature

5. Example: a 4.0 g sample of glass was heated from 274 K to 314 K, a temperature increase of 40 K and was found to have absorbed 32 J of energy as heat. What is the specific heat of this type of glass?

6. Heat of reaction – quantity of energy released or absorbed as heat during a chemical reaction (difference between stored energy of reactants and products)
Thermochemical equation – an equation that includes the quantity of energy released or absorbed as heat
Ex: 2 H2 (g) + O2 (g) 2 H2O (g) kJ

7. Enthalpy change (Δ H) – the amount of energy absorbed or lost by a system as heat during a process at constant pressure
ΔH = Hproducts – Hreactants
Negative for exothermic reactions and positive for endothermic reactions

8. Important things to remember
Coefficients represent # moles & can be written as fractions if need be
Physical state of reactants/products matters
Change in energy is directly proportional to number of moles reacting
ΔH is usually not significantly influence by changing temperature

9. Molar heat of formation – the energy released or absorbed as heat when one mole of a compound is formed by combination of its elements
When given for the standard state of that substance it is written as ΔH0f; the 0 is for standard state and the f for heat of formation

10. Substances that have a large negative ΔH0f are very stable
Small negatives or small positive ΔH0f are relatively unstable and will decompose easily
Large positive ΔH0f are very unstable and will decompose or react violently

11. Heat of combustion ΔH0c – the energy released as heat by the complete combustion of one mole of a substance

12. Calculating Heats of Reaction
Hess’s Law – the overall enthalpy change in a reaction is equal to the sum of the enthalpy changes for the individual steps in the process
If a reaction is reversed, the sign of ΔH is also reversed
Multiply the coefficients as needed

13. Example
Calculate the heat of reaction for the combustion of nitrogen monoxide gas to form nitrogen dioxide gas.
NO + ½ O2  NO2
From table A-14 on pg. 902:
½ N2 + ½ O2  NO ΔH0f = kJ/mol
½ N2 + O2  NO2 ΔH0f = kJ/mol

14. Heats of formation can be determined by combining the heat of formation and heat of combustion for various substances

15. Sect 17-2: Driving Force of Reactions
Most spontaneous reactions tend toward products that have a lower energy state than the reactants (exothermic reactions)
However, some endothermic reactions do occur spontaneously

16. Entropy (S) – a measure of the degree of randomness of the particles in a system
Reactants tend towards a less ordered state of matter (example: ice melting – liquid is less organized than solid)
In general, gases have the highest entropy, then liquids, and then solids
ΔS is postive for an increase in entropy and negative for a decrease in entropy

17. Free energy
Nature drives processes toward lowest enthalpy and highest entropy, when these are opposite directions, the dominant factor determines the direction
Free energy (G) – the combined enthalpy-entropy function
ΔG0 = ΔH0 - TΔS0

18. Example
For the reaction NH4Cl  NH3 + HCl at K, ΔH0 = 176 kJ/mol and ΔS0 = kJ/(molK). Calculate ΔG0, and tell whether this reaction can proceed in the forward direction at K.
+ 91 kJ/mol, so it does not occur naturally at this temperature

19. Sect. 17-3: The Reaction Process
Reaction mechanism – the step-by-step sequence of reactions by which the overall chemical change occurs
Intermediates – species that appear in some steps but not in the net equation
Homogeneous reaction – a reactions whose reactants and products exist in a single phase

20. Collision theory – set of assumptions regarding collisions and reactions
if collision is too gentle, the species rebound unchanged
If colliding species are poorly oriented, they will not react

21. Activation energy (Ea) – the minimum energy required to transform the reactants into an activated complex
Activated complex – a transitional structure that results from an effective collision and that persists while old bonds are breaking and new bonds are forming (not the same as intermediate)

22. activation energy for forward reaction
Activation energy for reverse reaction
Energy change in reaction

23. Sect. 17-4: Reaction Rate
Reaction rate – the change in concentration of reactants per unit time as a reaction proceeds
Chemical kinetics – the area of chemistry that is concerned with reaction rates and reaction mechanisms

24. Rate-influencing factors
Nature of reactants
Surface area
Temperature
Concentration
Presence of catalysts

25. Catalyst – increases rate of reaction with out being used up
Catalysis – action of a catalyst
Homogeneous catalyst – same phase as reactants/products
Heterogeneous catalyst – different phase as reactants/products

26. Rate law – an equation that relates reaction rate and concentrations of reactants for a reaction
If multiple steps in reaction mechanism, the slow step always controls the rate