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# #1: Thermochemistry

## Thursday, January 10, 2013 1:01 PM

Overview

- Chapter 3 - Sections 3.1-3.5 - Chapter 8 - Section 8.6 - Kinetic Energy -> Energy of moving objects -> e.g. Radiant, thermal. -> EKINETIC = (1/2)mv2 -> Eavg = 3RT/2NA -> Temperature is not thermal energy it is directly proportional to energy - Potential Energy -> Energy that is stored in position, composition, intermolecular forces or conditions -> E.G. chemical (bonds), mass (E=mc2), electrical (E= kq1q2/r) - Law of the Conservation of Energy -> Energy is neither created or destroyed -> Energy may be transferred or transformed -> 1st law of thermodynamics -> Transferred: energy moves from one place or thing to another. -> Transformed: Energy changes from one type to another.
- The area outside of where you are studying (Outside of the system) - Any area that's not the system

Energy (Measured in Joules) Section Excercises: 3.3.1, 3.3.2, 3.3.2 Figures: 3-4, 3-5, 3-2, 3-6

Terminology: Surroundings

Terminology: System

- The area, substance or compound that you are studying. There are three types: -> Open system: free exchange of energy and matter between the system and the surroundings - Example: Bowl of soup, beaker -> Closed system: exchange of energy but not matter between the system and the surroundings. - Example: Drink with a lid, stoppered flask -> Isolated system: no exchange of energy or matter between the system and the surroundings. - Example: Thermos of food, gas cylinder. - Thermal energy transfer from hot to cold between the system and the surroundings - May cause a temperature change or a phase change - Isothermal refers to a process at constant temperature (e.g. a phase change) ( T = Tfinal - Tinitial) - Measured in either Joules (J) or calories (cal) -> 1 Cal = 4.184 J -> calorie is the amount of heat needed to change the temperature of 1g water by 1 oC -> 1 Calorie = 1000 calorie = 1 kcal -> 1 J = 1kgm2s-2 -> 3.6 x 106 J = 1kWh

## Heat ( commonly called q)

Heat Capacity - C (JoC-1 - Amount of heat needed to change the temperature by 1 degree in the system or J/K) - heat capacities are proportionally constant between q and T - are compound specific Molar heat capacity CM (J/Kmol) - The heat capacity of 1 mol of substance

Specific heat capacity - - The heat capacity of 1g of substance Csp (Jg-1oC-1) - For water = 1 cal g-1 oC-C = 4.184 J g-1 oC-1 Question #1 A drink has 180 Calories. Given that an average 150 lb person uses 800 kJ/h while walking, how long must that person walk to not store any of the energy? (assume that all of the energy goes into walking no other things)! How long? Step 1 -> Convert from Cal to kJ Step 2-> Find the amount of time 7.53 x 102 kJ/ 800 kJ/h = 0.941 hr / 56 minutes Note: energy will flow from an area of high energy to low energy until both are the same temperature or energy level. Tsys < Tsurr nrg flows until Tsys = Tsurr Law of the conservation of energy Heat of reaction - qrxn - Energy is neiher created or destroyed - The total energy between the system and the surroundings, or of the universe, is constant - qsystem + qsurroundings = 0 - Amount of heat exchanged or transferred during a chemical reaction in a system between the system and its surroundings at constant temperature - Heat of combustion = Combustion reaction - Measured with isolated systems and thermometers. - amount of heat needed to change the temperature of the substance/compound - depends on the following:
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Quantity of heat = q = C T

## C T Practice examples: 3-1, 3-2

- depends on the following: -> Amount of temperature needed -> Amount of substance compound present -> Type of substance/compound - When positive, heat is absorbed or gained by the system - When negative, heat is released or lost by the system - qrxn < 0 that is, qrxn is negative (amount of heat needed to restore the original temperature) - Heat is produced - For isolated systems the temperature increases - For open or closed systems the heat is released into the surroundings - qrxn > 0 that is, qrxn is positive - heat is taken in - For isolated systems the temperature decreases - For open or closed systems the heat is removed from the surroundings. A 55.0 kg piece of metal was heated to 99.8 oC and then dropped into an insulated container with H 2O. There are 225 mL of water (Density = 1.00g/mL) at 21.0 oC present before the metal was added. The final temperature of the water and metal was 23.2. What was the specific heat of the metal assuming no heat transfer to the container or atm? You have 2 blocks of metal with volumes of 10 cm 3. One block is made of AL with a density of 2.698 gcm -3, specific heat ot 0.900 J/k/g and a temp. of 0oC. The other block is made out of Cu. The copper has a density of 8.933 g/cm 3 a specific heat capacity of 0.387 j/K/g and a T of 100 oC. If the two blocks are pushed together what will there dinal temperature be? What is the molar heat capacity for each metal. - Energy change by forces acting via distances - Tends to be pressure volume work - When w = negative, then energy is leaving the system - when deltaV = negative work is done to the system to decrease the volume (surroundings do work): work is positive - deltaV = positive, work is done by the system on the surroundings to increase the volume: work becomes negative - Units usually in Latm or J
- Is the total energy of a system and includes internal motion, bonds. Intermolecular attractions and the electrons that take part in chemical reactions - relationship between E and q, w is the first law of thermal dynamics deltaE = q + w - deltaE = 0 - have constant energy (isolated system - Have no exchange/transfer of heat or work - deltaE>0 - Have a positive change in internal energy (entering) - May have q > 0 or W>0 - deltaE<0 - Have a negative change in internal energy - May have q < 0 or w < 0

Exothermic

Endothermic

Question 2

Question 3

Work

Energy

Funtions Section 3.2.1, - Path-Dependant Functions 3.2.2, 3.2.3 - When arriving at the same state via different methods, the value of the property changes - For example, the value of q changes for liquid water depending on whether the liquid was formed from the solid or the vapour - Applies to work (w) - State Function - The value of the property is the same regardless of the method used to get the state - For example, the density of water is the same for water that came from ice or water that came from steam. - Applies to internal energy ( E ) and enthalpy (H) Bond Energies (Practice) Examples: 3-3, 3-4 Table:3-2 Section: 3.3.3 Calorimetry (Practice) Examples: 3-5, 3-6, 3-7 Section exercises: 3.4.1, 3.4.2 - Energy required to break 1 mol of chemical bonds in the gaseous phase - Also known as bond enthalpy and bond dissociation energy - Will always be positive in value for the breaking of bonds - For reactions it may be: - Exothermic - Stronger bonds in products than in reactants - Endothermic - Stronger bonds in reactants than in products Calorimetry - The isolated system used to determine quantities of heat where qrxn = -qcalorimeter - There are two types: -> Bomb Calorimeter -> Cofee-cup calorimeter (qv, constant pressure) - qcalorimeter is determined experimentally and is the amount of heat required to raise the temperature of the calorimeter by 1oC. Ccal = heat cpacity of the calorimeter. - Usually includes water inside the calorimeter - if not then -> qcal = qbomb + H2O Constant pressure/coffee-cup calorimetry you place 0.500 g of magnesium chips in a coffee cup calorimeter and add 100 mL of 1.0 M HCl. The reaction occuring in as follows: Mg + 2HCl -> H2 + MgCl2. The temperature of the solution increases from 22.2 C to 44.8C. What is the quantity of heat per mol of Mg? (Assume the specific heat in 4.20 the density is 1.00). A. quantity of heat = q = mCspDeltaT
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A. quantity of heat = q = mCspDeltaT m = HCl+Mg Q4 H Example: 8-8 Table: 8-5 Figure: 8-34 Estimate deltaE for the reaction: Ethane + air -> Carbon dioxide plus water A. Balance -> 2, 7, 4, 6 Enthalpy of vapourization - amount of energy needed to boil 1 mole of a substance Enthalphy of fusion - amount of energy needed to melt 1 mole of a substance Enthalpy of combustion - amount of energy needed to react 1 mol of substance with oxygen to from carbon dioxide and water Enthalpy of formation - amount of energy needed to from 1 mol of substance from its elements Note: Table are usually in the endothermic direction If a process of heat transfer in a chemical reaction, the amount of heat transferred in the heat of the reaction: H = Hf - Hi < 0 the H = -qp -> Exothermic H = hf - hi > 0 then H = -q -> endothermic Bomb calorimetry (Constant V) Chocolate chips cookies weighing 7.25 g are burnt in a bomb calorimeter to determine the E content. The heat capacity of the calorimeter is 39.97 KJ/C during the combustion the temperature rose by 3.90 C. Calculate the E contenct of the cookies in KJ/g Does this value match the nutrition label of 4 cookies(29g) = 150 cal How much heat is required to bring water, in the form of ice at 0C to steam @ 100C? hfus = 6.02 hvap = 440.7 Delta H naught formation Standard Enthalpy of Formation A substances enthalpy change in going from the standard state to the reference state The value is 0 if the substance is a pure element in the reference state or it is the ion H+ Standard state - the solid or liquid of the pure element or compound when the pressure is 1 bar (105 Pa close enough to 1 atm); commonly found in table format. (1bar, 1M, 298K Reference state - the most stable form of the element or compound. Standard state - Solid => Crystalline +pure, Liquid => normal, Gas => assume ideal Hof -> standard formation reaction enthalpy of the formation of 1 mol of molecules from their constituting elements when all the substances are in their standard state at the temperature of interest Formation reaction: Make 1 mol of the compound of interest Make from standard state or element reference Stated temp, pressure, concentreation Maybe exothermic or endothermic Eg. Hof [C(s, graphite) = o -> reference + standard state Hof [ C(s, diamond) = 1.895 kJ/mol => Standard state but not reference state Hof [ N2(g) ] = 0 reference + standard state may look up values in tables or calculate (Hess's Law) Ho and Hess's Law Practice examples: 3-9, 3-10 Section: 3.5.1, 3.5.2, 3.5.3 Standard Enthalpy of reaction -Ho or Horxn May be determined indirectly by Hess's Law or from the Hof. Enthalpy change when all the products + reactants are in their standard states at the temps of interest Note assume little to no change if near the standard reference states for Ho Hess's Law May indirectly solve for H by the manipulation of chemical equations for processes that occur in steps/stages Divide equation by x -> divide H by x Reverse equation -> change sign of H Add equations -> add H values How much energy is associated wit the electrolysis of H2O? 2H2O -> 2H2 + O2 Hrxn? A. Try looking in tables -> find: H2 + 1/2 O2 -> H2O H = -285.8 KJ Must reverse the rxn then double it Water -> H2 + 1/2 O2 x2 H = 571.6 kJ What is the enthalpy for the rxn used in/during welding? Fe2O3 + 2 Al -> 2Fe + Al2O3 = Products - Reactants = What is the enthalpy change for the fromation of methane from graphite and hydrogen gas? Given C + 2 H2 -> CH4 C + O2 -> CO2 H = -393.5 kJ H2 + 1/2 O -> H2O H = - 285.8 kJ CH4 + 2O2 -> CO2 + 2 H2O H= -890.3 kJ CO2 + 2 H2O -> CH4 + 2 O2 H = +890 kJ 2 H2 + O2 -> 2 H2O H = -571.6 kJ C + O2 -> CO2 H = -393.5 kJ
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Hof Appendix:D

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## Chem 1310 Page 4

#2 Thermodynamics
Thursday, January 24, 2013 1:43 PM

Spontaneity of Chemical Spontaneous Processes - Process or action that continues to occur without external Sections: 1-5 Chapter 11 stimulus once the action has been started Pages 610-654 - Reaction goes in the direction of disorder from order - REactions do not require constant input to occur. - Input -> Force or nergy or work put in Section 11.1.1, 11.1.2 Non-spontaneous - Process or action that requires constant external stimulus to continue - Reactions require constant input to occur - Trying to make order from chaos - Must do work, use energy or force NOTE: Spontaneitu is unrelated to exothermic/endothermic H or E may be compared. If a process is spontaneous then the reverse process is non spontaneous Entropy Examples: 11-13 Figures: 11-12 Is a state function with specified temperature pressure and compositions. S -> measurement of spontaneity ie. Of disorder or dispersion - Large S -> Large disorder - Smell S -> Small disorder - k = bottleman's constant = 1.38 x 10-23 J/K Ln = natural log - w = # of ways to constrain the system or order the system - system -> # of energentically equivalent states - If W = 1 then f = o, then the system is at perfection with no disorder. Measure of energy at a microscopic level - Particles may enter into energy levels/states different ways based upon the amount of energy in the system. - The more energy, the more states partially filled and the larger the amount of entropy - Based on Boltzmann's equation (S = klnW) and particles in a box. In general: - Increased T -> increased entropy - Increased # gas molecules by reaction -> Increased entropy - Increased disorder/motions -> increased entropy - ngas = nf - ni if ngas > 0 then S increases - if ngas < 0 then S decreases Predict if entropy increases or decreases a) CO2 (g) -> CO (s) S decreases because gas decreases. b) (s) -> (l) S increases Calculation of Entropy - For a reversible reaction: - A reaction that may change direction with a very, very small change in some property - minor changes in T,P,V eg transfer of heat out of the system at constant temperature to disorder the surrounding - rxn may be exothermic or endothermic but need to regulate
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## Entropy (S) Example: 11.2

- rxn may be exothermic or endothermic but need to regulate temp to keep is constant. - For a phase transition: - Normal boiling point of a non-hydrogen bonded organic liquid is usually around 87 JK-1mol-1 - Troutons Rule - To relate standard to non-standard: - Use a variation of the ideal gas law and Raoult's law to relate -> R = gas constant, P = pressure, c = concentration ,standard = 1 M / 1 bar -> if changing in rxns then: - to heat a compound from one temp to another use: - So -= standard molar entropy. Question 2 What is the entropy change for benzene (boiling) given that its enthalpy damage is 30.9 kJ/mol and that its normal boiling point is 80.1oC?

What is the change in entropy for water in going from ice at 0o to steam at 100oC. Given hfus = 6.02 kj/mol, hvap = 40.67 kJ/mol and Cmolar = 75.4 J/Kmol Second Law of thermodynamics All spontaneous processes/actions cause an increase in the entropy of the universe. An increase in entropy -> spontaneous reaction An decrease in entropy -> non spontaneous reaction When entropy is zero -> reaction is at equilibrium Need an increase in the entropy of the system or the surroundings (or both) for a reaction to occur spontaneously Commonly need to couple a rxn to the surroundings The entropy of a pure perfect crystal at 0K is zero Allows a reference point for the calculation of standard molar examples In general, more complex molecules -> increased So For the change in standard molar entropy of a reaction: The active ingredient in antiacid remides is CaCO3. Calculate the entrpy change in the formation of CaCO3 from its elevent. Does this value make sense? Is the following rxn spontaneous as written? CO(g) + 2H2 -> CH3OH at 25oC A. predictions increase S -> spontaneous => more complex molecule decrease S -> non spontaneous => ngas = -3 predictions conflict

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## Gibbs Free Energy (G)

A method of calculating the amount of energy present using information from the system
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## information from the system

Allows prediction of spontaneity of a reaction - G < 0 -> spontaneous in forward reaction - G = 00 -> reaction is at equilibrium under given conditions - G > 0 -> reaction is spontaneous in the reverse direction Reaction/process needs to be at constant temperature and pressure with only volume work possible as well as be 'reversible' May be related to the equilibrium Gof - standard free energy of formation - Is equal to zero when the element is in the reference form at P = 1 bar - The change in free energy in a reaction where a substance is made from the elemental reference forms. Go - standard free energy of a reaction - Is not an absolute value, is a relative value - Will change sign when the reactio is reversed - May add together several equations and their Go - to calculate under standard conditions:

Go - standard free energy change - To calculate under non-standard temperature: Go = Ho - TSo G - free energy change - Is the change in free energy under non-standard or non-ideal conditions - May be related to the reaction quotient (Q) and the equilibrium constant (Keq)
Requirements for spontaneous change: - The reaction/process has a forward and a reverse reaction - When the free energy decreases (G < 0), the reaction is spontaneous - Equilibrium between the forward and the reverse reaction occurs when G is at its lowest value At equilibrium, the thermodynamic equilibrium constant may be related to the free energy change: - Keq is the Kc or Kp in terms of activities (a)

Ho and Temperature

Clausius-Clapeyron equation - Often used to relate Ho and so to temperature and pressure - Is the equation of a straight line graph of lnP vs 1/T with m=slope = Ho/R and b = so/R - There are several ways to rearrage this equation mathematically and it is closely related to the van't hoff and the arrhenius equations

## Chem 1310 Page 7

#3: Kinetics
Thursday, February 7, 2013 1:27 PM

## Reaction Mechanisms Chapter 12

Mechanism requirements Each step needs to be consistent with the reaction stoichometry Needs to match the experimentally determined rate law Elementary Processes Are mechanisms steps Unimolecular if one molecule is involved Bimolecular if two molecules are involved Each step has a rate law (exponents from stoichiometry) May be reversible (at equilibrium) Reaction intermediates Do not appear in the overall chemical equation Produced and used in elementary processes May be isolated and have fully formed bonds Transition State Are not isolatable since they have partially formed bonds Exist at the point of the activation energy Rate Determining Step The slowest step out of several elementary processes Has the highest activation energy

Reactions Rate

Rate
- Speed or velocity of the change in the amount of reactant or product over time - Rate of formation Reaction is going forwards (formation of product) Positive rate - Rate of disappearance Reaction is going backwards (formation of reactant) Negative rate To determine the rate - Need to measure the amount of product formed or reactant used in a certain amount of time - May graph concentration versus time - May calculate using:

Several sets of values are averaged out Each set gives a tangent line on the graph allowing for the determination of an instantaneous rate of reaction When t is as small as possible and as close to zero as possible, this gives an initial rate of reaction. Rate Laws aA + bB -> dD + eE Reaction rate = k[A] m[B]n K = rate constant - Dependant on the reaction, the temperature and catalyst - Larger k value = faster reaction - Is a constant value at constant temperature - Units are dependant on the overall reaction order Exponents m and n = order - M or n = 0 gives zero order for m or n - M or n = 1 gives 1st order for m or n - M or n = 2 gives 2nd order for m or n - M + n = 1 gives pseudo - 1st order rxn - M + n = 2 gives 2nd order reaction Use initial rates or isolation experiments for rate order determination - Zero order Double concentration -> no rate change - First order Double concentration -> 2x the rate - Second order Double concentration -> 4x the rate - Third order Double concentration -> 8x the rate

## Zero Order Rate Law

A -> products M + n = 0 Rate law Reaction rate = k[A]0 = k (at constant Temperature) Graph of [A] vs time gives a negative straight line Units of k = molL -1 (time)-1 e.g. ms-1 Integrated rate law [A] t = -kt + [A]0
Half-Life:

## First order rate law

A -> products M +n = 1 Rate Law - Reaction rate = k[A] - Reaction rate = k[A]0[B] Graph of ln[A] vs time gives a negative straight line Units of k = (time) -1 Intergrated Rate Law ln[A] t = -kt + ln[A]0 Half life = 0.693/k = ln2/k Includes radioactive decay

## A -> products M + n = 2 Rate law:

- Reaction rate = k[A]2 Graph of 1/[A] vs time gives a straight positive slope
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Graph of 1/[A] vs time gives a straight positive slope Units of k = M-1(time)-1 e.g. Lmol-1s-1 Intergrated Rate Law Half-Life Working with Kinetics Practice: Section: Calculating reaction rates - Reaction rate = k[A]m[B]n - Graph to find a tangent line Calculation of reaction order - Initial rates, isolation experiments - Graph (different axis for straight lines) - Consistent t1/2 (only for first order) - Integrated rate laws Calculation of rate constant - Graph (slope) - Integrated rate laws - t1/2 (only for first order) Calculation of concentration or time - Integrated rate laws Mechanisms, Rates and temperature Practice: Section: Figures: Activation Energy (E a) - Minimum amount of energy needed by molecules to cause a chemical reaction - Is energy above that of the kinetic energy of the molecules Reaction rate is dependant on - Collision frequency - Percent of molecules with activation energy (related to temperature) - Molecular Orientation - Mechanism Arrhenius Equation: - Used to calculate the effect of temperature on reaction rate and activation energy - Data consistent with collisions between moleculs Effect of Catalyst Practice: Section: Catalyst - Speeds up the reaction by lowering the activation energy - Homogeneous catalysts are in the same phase as the reactants - Heterogeneous catalysts are in a different phase than the reactants - Enzymes are biological homogeneous catalysts

## #4: Principles and Applications of Chemical Equilibrium

Thursday, February 14, 2013 10:49 AM

Equilibrium Dynamic Equilibrium - Have two opposite reactions taking place at equal Practice: rates - Concentration of reactants and products remain constant with amounts dependent on the ratio of reactants products and the starting amounts - Neither the reactant or the product is completely used up - Examples include: Vapour pressure - same amount of vapour and liquid being formed Solubility - same amount of solid and dissolving and recrystallizing Equilibrium Equilibrium Constants - Dependent on temperature and the reaction Constants - Has a constant value for a given temperature Practice: - Solids and liquids have a value of 1 and do not change Sections: significantly during the reaction, thus they do not appear in the equilibrium constant expression K and the Reaction Quotient Practice: Reaction Quotient - Q - Predicts direction that the reaction goes to reach equilibrium: - Qc = 0 -> forward reaction, pure reactants - Qc < Kc -> forward reaction, more reactants and some products - Qc = Kc -> at equilibrium, rate of formation of reactants and products is constant - Qc > Kc -> reverse reaction, some reactants and more products - Qc = -> reverse reaction, pure products. Activities (a) - Used in relation of the thermodynamic equilibrium constant and Gibb's free energy - For solids or liquids in the standard reference state (i.e. pure), a = 1 - For gases: - For solutes and dissolved substances: K and Chemical Equations Practice: Section: If the chemical reaction is multiplied by some value -> K is brought to the power of that value If the chemical reaction is divided by some value -> the root of that value is taken for K If two chemical reactions are added together -> the K values for each are multiplied If the chemical reaction is reversed -> K is then inverted If K is very large (>10 8), the reaction goes to completion and no reactants are left, equilibrium not present If K is very small (<10-8), the reaction does not go and products are not formed, equilibrium not present If K is intermediate (10 -8<K<108), the reaction may be at equilibrium Eq'm and Requirements for spontaneous change: - The reaction/process has a forward and a reverse Thermodyn amics reaction - When the free energy decreases (G < 0), the reaction Practice: Figure: is spontaneous - Equilibrium between the forward and the reverse Section: reaction occurs when G is at its lowest value At equilibrium, the thermodynamic equilibrium constant may be related to the free energy change: - Keq is the Kc or Kp in terms of activities (a) - Allows for a relationship between K and the temperature (van't Hoff equation). Le Chatelier's Principle Equilibrium is shifted to offset changes in pressure, temperature or concentration. Concentration (n/V) Equilibrium shifts in the direction in which the new concentration amount is used up Temperature (T) Increased T = heat addition -> shifts in the

Activities Practice:

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Increased T = heat addition -> shifts in the endothermic direction (H=+) Decreased T = heat removal -> shifts in the exothermic direction (H = -) Pressure (P) Increased P by added reactant or product -> equilibrium shifts in direction required to use the new amount Decreased P by removal of reactant or product -> equilibrium shifts in direction to make more Changing P by non-reactive gas -> no effect on K Constant P by non-reactive gas -> equilibrium shifts to side with the fewest moles of gas Increased P by decreased volume -> equilibrium shifts to the side with the fewest moles of gas Decreased P by increased volume -> equilibrium shifts to side with the most moles of gas Catalyst - Equilibrium is achieved faster Equilibrium K from equilibrium concentrations or pressures Calculation K from initial concentrations or pressures s Initial concentrations from the K Equilibrium concentrations or pressures from K Equilibrium concentrations or pressures from K without knowing directions of the equilibrium Types of Proton Transfer Aqueous Acids and Bases Equilibria Gives Ka for acids and Kb for bases and other Solubility terminaolo Ionic solids gy Gives a Ksp Complexation Complex ions made in formation reactions Gives a Kf Spectator ions Solubility Soluble Solid that dissolves in water, measured in quantity per and volume Precipitatio Have a solubility product constant (Ksp) n Things may also be slightly soluble or insoluble depending on the value of Ksp Precipitation Formation of solid from ions that were previously soluble in solutions Predict using K vs Q Q<K -> prceed towards products = unsaturated solution Q=K -> is at equilibrium = saturated solution Q>K -> Proceed towards reactants = supersaturated solution Common Ion Effect Occurs when an ion is common between dissolved compounds Causes a shift in the equilibrium in the direction that does not contain the ion that is shared between the dissolved compounds Ionization suppression occurs in a weak electrolyte via the addition of the ionization product Is a solution that Has very little change in pH upon the addition of acid or a base Is able to Be a base Be an acid Not neutralize itself Has weak acid and conjugate base present pH and changes in pH may be calculated using the Henderson-Hasselbalch equation or standard equilibrium calculations pH = -log[H] and pK - log K Buffer Capacity Refers to amount of acid or base that can be added/neutralized before the buffer solution stops being a buffer Usually an excess of the buffer solution is used in relation to the amount of acid or base added Buffer Range Is the pH range in which the buffer solution acts as a buffer Usually the range is approximately 2 pG units Acidic Buffers Weak acid with strong base -> conjugate base and weak acid Weak acid with conjugate base salt -> weak acid and conjugate base Basic Buffers Weak base with strong acid -> conjugate acid and weak base Weak base with conjugate acid salt -> weak base and conjugate acid.

Buffer Solutions

## Acid, Bases and Titrations

Tuesday, April 2, 2013 10:47 AM

## Intro Acid and Base Theories

Chapter 14, sections 14.1-14.7, chapter 15, section 15.3 Arrhenius Theory - 1884 Assumes all acids have H+ and all bases have OH Strong electrolytes dissociate completely upon dissolving Weak electrolytes dissociate partly upon dissolving Neutralization makes water Bronsted-Lowry Theory - 1923 Acids are proton (H+) donors and bases are proton acceptors Neutralization may make water or salts Lewis Theory Lewis acids accept an electron pair via an empty orbital whereas Lewis bases donate an electron pair Conjugate acid - Acid formed by the addition of a proton to a base Conjugate base - base formed by the removal of a proton from an acid Conjugate pair - set of base and corresponding conjugate acid or vice versa. Amphiprotic - compound that may accept or donate a proton, may be an acid or a base. Polyprotic - compound that may donate more than one proton per molecule Monoprotic - compound that is capable of only donating or accepting 1 proton per molecule Strong acids and bases ionize or dissociate completely Weak acids and bases ionize/dissociates partially Are at equilibrium favoured side based on relative strengths Acid Ionization constant Ka Base Ionization constant Kb Water may self-ionize/autoionize Ion product of water (Kw) Hydronium ion = H3O+ = essentially the same thing as H+ Kw = [H3O+][OH-] = 1.0 x 10-14 M at 25oC Kw = (Ka)(Kb)

Bronsted-Lowry Theory

Ionization

pH, pOH, pK

pH Method of describing [H3O+] Potential of hydrogen ion pH = -log[H3O+] [H3O+] = 10-pH pOH = -log[OH-] [OH-] = 10-pOH pK = - logK K = 10-pK pKw = pH + pOH = 14.00

Percent Hydrolysis and Salts Percent ionization or percent dissociation or percent hydrolysis Strong acids/bases are 100% ionized Weak acids/bases have increased ionization at lower
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Weak acids/bases have increased ionization at lower concentrations Salts Strong acid + strong base -> no pH effect Strong acid + weak base -> acidic effect Weak acid + strong base -> basic effect Weak acid + weak base -> depends on Ka and Kb Structure and Recognition Molecular structure relationship to strength Oxyacids Carboxylic acids Binary acids Amines Zwitterions

Neutralization Reactions and Titration Curve Titration Curves Plot of pH vs amount of titrant added Titrant The solution that is added to the beaker where the neutralization reaction takes place/has indicator End Point When the indicator changes colour Equivalence or Stoichiometric point When the stoihciometric amount (in mol) of acid is the same as the amount of base (neither are in excess) Mid Point When the amount (in mol) of titrant is 1/2 that of the solution Also known as the half equivalence point Indicators Display colour changes with different pH's Very little is required and used Need ~90% in the acid or base form to get that colour and may have intermediate colours May be prepared as a paper or as a solution Is approximate pH Standardization To find the solution concentration by the use of another solution with a known concentration Strong acid + Strong base Drastic change in pH at the equivalence point Weak acid + strong base Has an acidic buffer region with a less drastic change in pH at the equivalence point Weak acid + weak base Has an acidic buffer region and a basic buffer region and is difficult to identify the equivalence point Weak polyprotic acid + strong base Has multiple acidic buffer regions and more than one equivalence point

## Chem 1310 Page 13

Electrochemistry
Tuesday, April 2, 2013 12:10 PM

Redox Reactions

Redox reactions Couple an oxidation reaction to a reduction reaction Oxidation Compound loses e- and is called the reducing agent Occurs at the anode and usually results in the formation of a cation/compound with a higher oxidation number. 1. Identify oxidation, reduction reactions and assign oxidation states 2. Write chemical equations for species with changing oxidation numbers 3. Mass balance the equations (2) - Ensure the same number and type of atoms on each side of the reaction - For acids, use H2O for oxygen and H3O+ for hydrogen - For bases, use H2O for hydrogen and then OH - for oxygen or balance as per acid and then replace H + with OH-. 4. Charge balance the equations from (3) 5. Make sure an equal number of e - are transferred between the two reactions 6. Add and simplify the redox reaction
Electrochemical Cell - Formed when two half cells are connected together by a salt bridge and a wire/voltmeter between the two electrodes Electrode - Where the chemical half reaction takes place Half cell - contains everything required for the half reaction Voltmeter - device to measure current between the two half cells Salt bridge - allows spectator ions to travel between the two half cells Potential - direction of the spontaneity of the redox \ reaction Cell voltage - difference in potential between the two half cells If it is positive then it is spontaneous in the forward direction Also called electromotive force or cell potential Standard hydrogen electrode - SHE Chosen to have zero (0) potential All half cells are measured relative to it Forward reaction = reduction Cell diagrams - shorthand notation Line for phase boundary, double line for salt bridge, commas for different ions/species in solution Oxidation/anode first, then reduction/cathode Voltaic or galvanic Cell Chemical reaction is sponteaous Generates current and may run a device Electrons run clockwise from anode to cathode Electrolytic Cell Chemical reaction is non-spontaneous Requires current to run Electrons run counter-clockwise from the cathode to the anode

## Balancing Redox Reactions

Cells

Potentials

Standard Electrode Potential Measurement of the reduction potential of an electrode in a 1M solution/1 bar of gas at the temperature of interest while all substances are in their standard state relative to the SHE. SHE is set as the anode while the electrode compound tested is made to the cathode Standard Cell potential Difference in potential between two standard electrode half cells. A positive value indicates that the reaction is spontaneous

1:36 PM