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Thermochemistry
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The study of heat changes in chemical reactions Exothermic: reactions that release heat Endothermic: reactions that absorb heat Enthalpy: the heat content of a system at constant pressure
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Units of Heat 1 Calorie = 1 kilocalorie = 1000 calories 1 J = 0.239 cal 4.186 J = 1 cal Food Calorie
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Heat Capacity The heat capacity of an object depends on: – mass – chemical composition. The amount of heat needed to increase the temperature of an object exactly 1°C is the heat capacity of that object.
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Specific Heat q = mcΔT Where: q = heat (energy) m = mass c = specific heat ΔT= temperature change
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Specific Heat of Substances
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Why is the sand hot and the water cool at the beach?
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Jet Stream
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Enthalpy The heat content of a system at constant pressure is the same as a property called the enthalpy (H) of the system.
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Calorimetry The measurement of heat changes for physical and chemical processes
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Calorimetry
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Two Key Equations 1. q reaction = -q surroundings q r = -q s 2. q = mcΔT = ΔH Where:m = mass c = specific heat ΔT= temperature change
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Calorimetry Example 1.50 mL of water is placed in a beaker. A piece of calcium is weighed and placed in the cup. The temperature change of the water is measured. Calculate the heat released to the water by the calcium. Note: c = 4.184 J/g°C 2. Calculate the heat released per mole of calcium based on the previous results
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Thermochemistry Exothermic reaction: Heat is a product C 3 H 8 + 5O 2 → 3CO 2 + 4H 2 O + 2043 kJ ΔH = -2043kJ H Reaction Progress (t)
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Thermochemistry Endothermic reaction: Heat is a reactant C + H 2 O + 113 kJ → CO + H 2 ΔH = +113kJ H Reaction Progress (t)
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Enthalpy (ΔH) Heat content of a system at constant pressure ΔH = H products - H reactants ΔH ◦ is the standard enthalpy reported at 25 degrees C and 1 atm. Sign of ΔH ProcessHeat +endothermicabsorbed -exothermicreleased
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Standard Heats of Formation For a reaction that occurs at standard conditions, you can calculate the heat of reaction by using standard heats of formation.
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Standard Heats of Formation
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Entropy and Reaction Tendency There is a tendency in nature to proceed in a direction that increases the randomness of a system. A random system is one that lacks a regular arrangement of its parts. This tendency toward randomness is called entropy. Entropy, S, can be defined in a simple qualitative way as a measure of the degree of randomness of the particles, such as molecules, in a system.
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Standard Entropy Changes for Some Reactions
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Entropy In a solid, the particles are in fixed positions, and we can easily determine the locations of the particles. In a liquid, the particles are very close together, but they can move around. Locating an individual particle is more difficult. The system is more random, and the entropy is higher. In a gas, the particles are moving rapidly and are far apart. Locating an individual particle is much more difficult, and the system is much more random. The entropy is even higher.
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Entropy Absolute entropy, or standard molar entropy, of substances are recorded in tables and reported in units of kJ/(molK). Entropy change, which can also be measured, is defined as the difference between the entropy of the products and the reactants. An increase in entropy is represented by a positive value for ∆ S, and a decrease in entropy is represented by a negative value for ∆S.
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Free Energy Processes in nature are driven in two directions: toward least enthalpy and toward largest entropy. As a way to predict which factor will dominate for a given system, use this equation: ∆G 0 = ∆H 0 – T ∆ S 0 This combined enthalpy-entropy function is called the free energy, G, of the system; it is also called Gibbs free energy.
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Relating Enthalpy and Entropy to Spontaneity ∆G 0 = ∆H 0 – T ∆ S 0 A spontaneous reaction is one that goes to completion unaided Example: rusting, ice melting
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