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Solute, solvent, dissolution, precipitation, solubility, molarity, molality, mole fraction. Solute: substance in smaller proportion. Solvent: substance in greater proportion. Dissolution: process of dissolving. Precipitation: reverse of dissolution. Solubility: amount solute to saturate solvent.
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Solutions: Terms
Molarity: moles of solute per liter of solution. Molality: moles of solute per kg of solvent. Mole fraction: fraction of moles of given substance relative to total moles in solution.
Xa = na/n
What is an electrolyte? Free ions in a solution conducts electricity. What is the vant Hoff factor, i? Number of ions existing after dissolution of one unit of substance: NaCl, CaCl2
Vapor Pressure
Definition? Sometimes a tough concept pressure exerted by the gaseous phase of a liquid that evaporated from exposed surface of liquid. My definition: pressure exerted by molecules leaving liquid phase on the atmosphere lets draw what I mean!
Vapor Pressure
Vapor Pressure
Think about my definitionwhat property of the liquid will determine vapor pressure? Intermolecular forces! High ones will hold liquid in liquid form and decrease pressure exerted by molecules leaving liquid. Low ones will allow liquid to escape into gaseous form and increase pressure exerted by molecules as they change phase volatile.
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What is the law called that describes this situation? Raoults Law: Pa = XaPa*where * is pure A.
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bimolecular
2NO2
termolecular unlikely!
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Activation Energy, Ea
Activation energy is the extra kick of energy that a reaction needs to proceed. MCAT loves Ea diagrams, but first, what are exothermic and endothermic reactions? Two diagrams, one for each above type:
Ea R H _ P
Ea R H +
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Activation Energy, Ea
From the activation energy concept, three statements can be made:
low Ea fast reaction rate. more reactants fast rate (more collisions possible). higher temperature fast rate (more reactant molecules have sufficient kinetic energy to overcome Ea).
Ea1 Ea2
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Catalysts
What is a catalyst? Substance that makes reaction go faster by speeding up rate-determining step or providing an optimized route to products. Reactant vs. catalyst catalyst unchanged at end of reaction. Catalysts change rate, not thermodynamics (G, H, S, etc.).
Ea
Ea,cat
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Rate Laws
What does a rate law tell us? The rate at which a reactant disappears. Consists of rate constant, and concentrations of reactants in slow step only!! Rate laws determined experimentally. aA + bB cC + dDrate law?
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Rate Laws
Rate = k[A]x[B]y x order of rxn with respect to A. y order of rxn with respect to B. x+y overall order of reaction. k rate constant. Note: cannot get orders of reactants or rate constant from balanced equation. Need to look at experiment to get rate law.
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Rate Laws
A+B+C D+E
Experiment 1 2 3 4 [A] 0.2 M 0.4 M 0.2 M 0.2 M [B] 0.1 M 0.1 M 0.2 M 0.1 M [C] 0.05 M 0.05 M 0.05 M 0.1 M Initial Rate, Ms1 1 103 2 103 4 103 1 103 21
Rate Laws
Look at two experiments where only one reactant concentration changes. Determine the factor by which it changes, and compare to factor by which rate changes. order 1. [A] doubles rate doubles [B] doubles rate quadruples order 2. [C] doubles rate uneffected order 0.
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Rate Laws
When order is 0, rate does not depend on concentration of reactant. Rate law for this example: k[A][B]2 Determining kanyone remember the formula for finding k? Solve the rate lawk = rate/[A][B]2 Substitute numbers from any experiment for [A] and [B].
k = 1 103 / 0.2 (0.1)2 = 0.5 Ms1
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Mass-action ratio ratio of products to reactants: [C]c[D]d Keq = [A]a[B]b Gases and aqueous molecules only!!
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Le Chteliers Principle
What does Le Chteliers principle state? A system at equilibrium will try to neutralize any imposed change (stress) in order to reestablish equilibrium. The effects of different stresses:
Addition of product or reactant. Removal of product or reactant. Changing volume and temperature. Adding inert gas and adding catalyst.
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Le Chteliers Principle
N2 (g) + 3 H2 (g) 2 NH3 (g) + heat Adding or removing N2 Adding or removing NH3 Reducing volume? Increasing volume?
cut volume, raise pressure favor fewer moles raise volume, decrease pressure favor greater moles.
Changing temp? Adding or removing heat. Inert gas and catalyst no change (catalyst changes rate of forward and reverse equally).
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Solubility Product
How is the solubility product constant defined? The extent to which a salt will dissolve in water. Ksp is determined just like Keq. Solubility product constant is also temperature dependent. MnXm(s) nMx+(aq) + mXy(aq) Ksp = [Mx+]n[Xy]m
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Amphoteric Substances
What is an amphoteric substance? A substance that can act as either an acid or a base. Where does this happen? Polyprotics! When a substance has more than one proton to donate, the conjugate base can either donate another or accept a free proton. H3PO4 H2PO4 + H+ HPO42 + 2H+
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Anyone know the term for this equilibrium? Autoionization of water Kw = [H+][OH] Value of autoionization constant at 25 C? Kw = 1.0 1014as in pH + pOH = 14
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pH Calculations: A Shortcut
Normal formula: pH = log[H+]also, pOH = log [OH] Great when [H+] = 1 102 pH = 2 But how about when [H+] = 2.3 104 M? Use this shortcut
if [H+] = y 10n M (where n is a whole number). then pH is between (n1) and n.
pH Calculations
Remember the shortcut for estimating pH from [H+]. When looking at weak acid (base), given its initial concentration, use the ICE method to find [H+] and pH. What is pH of 0.2 M solution of HCN?
Ka = 4.9 1010
Neutralization Reactions
What is a neutralization reaction? When an acid and base react to form a salt and water. Like when you take antacid (Tums, etc.). A handy formula for complete neutralization: a [A] Va = b [B] Vb
a is # acidic H, b is # Hs base can accept. [X] is acid/base concen. and V is volume.
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Neutralization Reactions
How much 0.1 M NaOH solution needed to neutralize 40 mL of 0.3 M HCl? HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l) a [A] Va = b [B] Vb 1 0.3 40 = 1 0.1 Vb Solve for Vb to get 120 mL. Remember the formula to get you out of jamsworks with neutralization reactions only to save time over the ICE method.
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Indicators
An indicator marks the endpoint of a titration, but why does it change color? Indicator is actually weak acid whose protonated form is one color and deprotonated is another. How does this help us? Dont forget that the indicator is a weak acid!
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Indicators
HIn H+ + In Ka = [H+][In]/[HIn]now rearrange: [H+]/Ka = [HIn]/[In]and look at ratios:
If [H+] Ka, [HIn] [In]see color 1 If [H+] = Ka, [HIn] = [In]mix of two colors If [H+] Ka, [HIn] [In]see color 2
Picking an Indicator
When picking an indicator, use one whose pKa value lies within the pH range that you want to detect. For indicator, pKa +/ 1 represents effective range for color change. So dont expect to detect a pH change from 3 to 4 if your indicator has a pKa of 8 or 9!
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Hydrolysis of Salts
The reaction of a substance (salt/ion) with water is a hydrolysis reaction. Questionwill the hydrolysis result in a neutral, acidic, or basic salt? NaCl in water neutral because neither Na+ nor Cl will react with water:
Cl is conjugate base of a strong acid. Na+ is conjugate acid of a strong base.
NH4Cl in wateracidic because NH4+ will react with water (it is a weak acid).
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Hydrolysis of Salts
NH4CN in waterNH4+ is weak acid, but CN is good base, so which wins?? Need to know Ka/Kb values! Ka for NH4+ = 6.3 1010 Kb for CN = 1.6 105 Solution will be basic because CN is better base than NH4+ is an acid.
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What is a buffer?
A solution that resists changing pH when a small amount of acid or base is added. The resistance comes from the presence of a weak acid or base and its conjugate in roughly equal concentrations. An expression to remember: Ka = [conj. + [H ] base] [acid]
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Buffer Compensation
A biochemical example: the blood. The main buffer: carbonic acid: CO2 + H2O H2CO3 H+ + HCO3
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Buffer Compensation
Compensation critical to prevent medical disorders like acidosis and alkylosis. Essentially Le Chteliers principle at work. Addition of small amount of acid like HCl causes added H+ to react with present HCO3 to form H2CO3. Equilibrium has shifted to the left, but existing H2CO3 prevents large change in pH (compensation reverses effects).
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Buffer Compensation
Provided that acid and its conjugate are in similar concentration, the pH change is minimal. Addition of small amount of base like KOH causes added OH to react with present H2CO3 to form HCO3. Equilibrium has shifted to the right, but existing HCO3 prevents large change in pH (compensation reverses effects).
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If [A] = [HA], then pH = pKa An ideal buffer works under these conditions. Small changes to the ratio are acceptable, but the ratio should stay near 1.
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HIn In
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Buffer!
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By H-H equation, the pH at half equiv. must be equal to pKa this allows identification of unknown. Types of Curves:
Slope to upper right SA+SB, WA+SB Slope to lower right WB+SA Polyprotic acids have multiple equiv points (why?)
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Titration Curves SA + SB
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Titration Curves WA + SB
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Titration Curves WB + SA
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What are some situations in which entropy is predictable? Liquids have more than solids, gases more than liquids, particles in solution more than solids, two moles more than one mole.
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More Enthalpy
Each reaction has own H doubling reactants will double the heat required or released. Hesss Law of Heat Summation, Remember? If a reaction occurs in several steps, the sum of the energies absorbed or released in all steps will be the same as the overall reaction. If reaction is reversed, the sign of H reverses too. If equation multiplied by constant, so too is H.
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CH4(g)
2O2(g)
Hrx = H3
CO2(g) + 2H2O(g)
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G and Temperature
G = H TS
H S G Reaction is Spontaneous Spontaneous Non-spontaneous Non-spontaneous Spontaneous Non-spontaneous 82
+ +
+ +
Reversibility: the reverse of any reaction has the same magnitude for all thermodynamic values (opposite signs) and the same reaction pathway:
Coming from products side, Ea is now forward Ea plus Glook at the graph.
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Should you know this equation? Probably not, but know this for sure
G < 0 spontaneous Keq > 1 G = 0 at equilibrium Keq = 1 G > 0 non-spontaneous Keq < 1
Quick summary: for a spontaneous reaction, products are favored; for non-spontaneous reaction, reactants are favored.
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Oxidation-Reduction Reactions
Oxidation number: how many electrons an atom is donating or accepting in moleculaar bonding. Oxidation-reduction (redox) reaction: reaction in which oxidation numbers of reactants change. LEO says GER, LEO the GERman, OIL RIG
Oxidation is loss, Reduction is gain of electrons.
Reducing agent causes reduction and is oxidized. Oxidizing agent causes oxidation and is reduced.
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Harnessing flow of electrons from redox reaction to generate an electric current. Red cat, an ox Reduction @ cathode; oxidation @ anode. 86
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Nernst Equation
2.303RT 0.0592 V logQ = E logQ E = E nF n Electrode potentials for non-standard conditions, but T still = 298 K. Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) [Zn2+] 0.0592 V log E = E 2 [Cu2+]
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Electrolytic Cells
Unlike a galvanic cell, electrolytic cells use an external voltage source like a battery to create an electric current that forces a non-spontaneous redox reaction to occur electrolysis. Electroplating: plating a thin layer of metal on top of another material application of electrolytic cells, often done in coin mints or with jewelry. Red cat, an ox still applies!
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Concentration Cells
A galvanic cell that has identical electrodes but whose half-cells have different ion concentrations. Electric current from potential difference arising from unequal concentrations. Electrons will flow in direction of highest concentration of positive ions. When concentrations of solutions become equal, the reaction will stop.
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Concentration Cells
[Ni2+]dilute