Chemical Reactions: Energy, Rates and Equilibrium

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1 Chemical Reactions: Energy, Rates and Equilibrium Chapter 7 Heat Changes During Chemical Reactions Bond Dissociation Energy- The amount of energy that must be supplied to break a bond and separate the atoms in the gaseous state Bond breaking requires energy Triple bond > double bond > single bond Bond making releases energy The difference between the bond breaking and bond making energies is called the heat of reaction or the enthalpy change, denoted by: ΔH 1

2 Exothermic and Endothermic Reactions Exothermic Reaction - A chemical reaction in which energy is released as the reaction occurs The products have lower energy than the reactants The chemical bonds that are broken in the reactants are weaker than the chemical bonds that are formed in the products Endothermic Reaction - A chemical reaction in which energy must be supplied overall to get the reaction to occur The products have a higher energy than the reactants The chemical bonds that are broken in the reactants are stronger than the chemical bonds that are formed in the products Examples of Exothermic and Endothermic Reactions Exothermic: ΔH is a negative value Endothermic: ΔH is a positive value 2

3 Why Chemical Reactions Occur? Two factors determine if a process proceeds on its own without any external influence Enthalpy, ΔH Entropy, ΔS Entropy: A measure of the amount of disorder or randomness in a system Entropy increases as physical state changes from solid to liquid to gas Entropy increases when the amount (moles) of products increases compared to the reactants Free Energy, ΔG Free Energy, ΔG, takes into account the contributions by ΔH and ΔS If ΔG is negative, free energy is released and the process is spontaneous, exergonic If ΔG is positive, free energy is absorbed and the process is non spontaneous, endergonic 3

4 Evaluating ΔG ΔG = ΔH - TΔS A process will always be spontaneous (ΔG<0) if Δ H<0 (favorable) and ΔS>0(favorable) A process will always be nonspontaneous (ΔG>0) if ΔH>0 (unfavorable) and ΔS<0 (unfavorable) A process may be spontaneous (ΔG<0) if ΔH<0 (favorable) and ΔS<0 (unfavorable) or ΔH>0 (unfavorable) and ΔS>0 (favorable) depending on the temperature, T due to - TΔS term Collision Theory and Chemical Reactions Collision Theory For a chemical reaction to occur, the reactant molecules must collide with each other Not all collisions lead to a chemical reaction The molecules must have a proper orientation for the reaction to occur The collision must occur with sufficient impact to overcome the activation energy (E act ) barrier Activation Energy- The minimum amount of kinetic energy the reacting molecules must possess for their collision to produce a chemical reaction 4

5 Orientation of Reactants Exergonic and Endergonic Energy Diagrams 5

6 Factors Influencing the Rate of a Reaction The nature of the reactants If strong bonds have to be broken, the reaction rate is slower The physical state of the reactants The concentration of the reactants Higher concentration leads to more collisions per second The temperature At higher temperatures, the average kinetic energy of the reactants is greater A larger percentage of the collisions have sufficient energy to overcome the activation energy barrier The presence of a catalyst Catalyst- A substance that increases the rate of a reaction without appearing in the overall balanced equation Lowers the activation energy barrier Effect of a Catalyst 6

7 Chemical Equilibrium Chemical Equilibrium - a situation in which two opposing chemical reactions occur at the same rate. The chemical reaction must be reversible The chemical reaction must not go to completion Often occurs for chemical reactions in the gas phase in a closed container or for reactions in solution A double arrow is used to indicate chemical equilibrium Reaction Rates at Equilibrium Forward and reverse reactions DO NOT stop Forward and reverse reaction rates become equal 7

8 Equilibrium Constants aa + bb + <===> mm + nn + Equilibrium constant relates the relative amounts of the products and reactants Magnitude of the Equilibrium Constant The value of the equilibrium constant indicates which reaction (forward or reverse) is favored K >1 favors products, K<1 favors reactants 8

9 Le Chatelier s Principle Le Chatelier s Principle- If a stress is applied to a system at equilibrium, the equilibrium will shift in such a way as to partially remove the stress Change in concentration Change in temperature Change in pressure (if gases are involved) Addition of a catalyst Effect by Change in Concentration Consider the following reaction: CO (g) + 2 H 2 (g) <===> CH 3 OH (g) What happens if more CO is added after equilibrium has been achieved? 9

10 Forcing a Reaction to Completion By continuously removing product as it is made the reaction continues in the forward direction until all of the reactants are used Effects by Changing Temperature Reversible reactions are endothermic in one direction and exothermic in the other direction Endothermic (heat absorbing) reactions will be favored by increasing the temperature Exothermic (heat releasing) reactions will be favored by decreasing the temperature 10

11 Effects by Changing Pressure Increasing pressure for reactions involving gases favors the side with the fewer number of moles of gas Effect by Adding a Catalyst Adding a catalyst only speeds up how fast equilibrium is achieved Adding a catalyst DOES NOT change the equilibrium constant therefore the concentrations at equilibrium will be unchanged 11

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