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GRAVIMETRICS (aka calculations involving stuff you weigh/ mass)

Chapter 3 (Stoich); 4 (Aqueous Soln); 10 (Gases): 13 (Colligative Props)
Density = mass/ volume Moles = mass/ molar mass Kelvin = 0Celsius + 273

D = m/V n = m/ MW K = 0C + 273

Recall 1 mole = Molar mass (g) = 6.02 x 1023 representative particles (atoms, molecules, formula units, etc.)

= 22.4 L for gases only at STP (00C and 1 atm) Remember mass conservation: A + B C If you have gA and gC, then gB = gC gA (remember your labs!)

% Composition problems

(Note: Hydrate & Combustion analysis problems are a version of this.)

if needed, change % g (assume 100 g sample) convert g mol (use periodic table (PT) for molar mass) divide all mol by smallest # of moles to get molar ratio if needed, multiply by a whole # to get whole # ratios (ex. If a # ends in .33which is 1/3, x 3; if # ends in .5 which is 1/2, x 2) EMPIRICAL FORMULA if molecular mass is given, divide the molecular mass by the empirical formula mass to get a whole number; multiply the subscripts in the empirical formula by this number MOLECULAR FORMULA

Basic Stoichiometry questions

Know how to BALANCE equations before doing any stoichiometry if needed, convert what you are given/ begin with to moles (since all chemical equations are in terms of moles, not mass) use either the FORMULA or the coefficients in the CHEMICAL EQUATION to convert to moles of the substance you want/ asked for in the question if needed, convert from moles of what you want to the units you want using molar conversions

Limiting reagents (Key words: reaction goes to completion you can also use a BCA table
When given more than one REACTANT amount, you have to determine which one is limiting before you do any further calculations You will be doing two calculations for each method since you have two reactants; if there are more reactants, you would have to do more calculations (ex. if there were 4 reactants, I would have to do 4 calculationsone for each reactant) Method 1 -starting with each reactant, do a stoich calculation to g of product -the REACTANT that gives you the smallest theoretical yield of product is the limiting reactant; the other reactant is the excess reactant -the maximum amount of product that can be made is the amount calculated from the limiting reactant Method 2 (often used with BCA tables) -convert each reactant to moles -divide each of the moles by the coefficient in the equation to get the number of reactions -the REACTANT that gives you the smallest number of reactions possible is the limiting reactant; the other reactant is the excess reactant

Measuring the Concentration of Solutions (aqueous and gaseous)

Molarity = moles solute/ Liters solution molality = moles solute/ kg solvent

M = n/V m = n/ kg

used a lot in colligative prop problems (freezing pt/ boiling pt changes in solns)

*To convert from molal to molar, need to get liters of SOLUTION: the mass of solute + mass of solvent = total mass of solution; total mass of solution density = volume of solution *To convert from molar to molal, need to kg of solvent: liters of solution x density of solution = total mass of solution; total mass of solution mass of solute (from moles) = mass of solvent Dilution equation (a small sample of concentrated solution containing a certain number of moles solute is placed in more water to make a more dilute solution; the number of moles solute stays the same) moles conc. Molarity x Volume (concentrated) = = moles dil. Molarity x Volume (dilute)

n1 = n2 M1 V1 = M2V2

(M=n/V so n= MV)

*The volume unit can be in any unit for the dilution equation as long as you are consistent on both sides. Mole fraction of A = moles A/ total moles XA = nA/ ntotal where ntotal = (nA + nB + nC + ) used a lot in colligative prop problems (Raoults law of vapor pressure lowering) used a lot in gas problems (Daltons law of partial pressure) Mass percentage = (mass of component/ total mass) x 100% Parts per million, ppm = mass of component in mg/ mass of solution in kg

*rarely used in Gen Chem

Titrations (used to determine unknown concentrations) MA x VA nA nB VB MB

-involve the use of a buret (containing reactant A) and an Erlenmeyer flask (containing reactant B) -typically, A is added to B until a titration endpoint is reached (enough B has been added to use up all the A without leaving an excess amount of B); an indicator is oten used to determine when the reaction is complete Ex. I31- + 2 S2O32- 3 I- + S4O62- (2 ions of S2O32- would have to be added for every 1 ion of I31-) (a starch indicator is used; it is blue when bound to I31-and becomes clear when all I31- is changed to I-) -sometimes, less B is added A and a limiting reagent calculation must be done to determine the extent of the reaction

Solutions
Substances with similar intermolecular forces tend to be soluble in each other; Like dissolves like, which means polar solvents dissolve polar solutes; nonpolar solvents dissolve nonpolar solutes. Pressure affects the solubility of GASES only. Henrys law Concentration of gas in solution = Henrys law constant* x Partial pressure of gas over the solution

Mgas = kH Pgas
*kH is a constant that depends on the temperature and particular solute and solvent combination; it has the same value as long as the temp, solute, and solvent remain the same; it changes if any of those factors changes

3 Temperature generally increases the solubility of solids, but decreases the solubility of gases:

Gases = NH3, SO2, (HCl, sometimes)

Colligative Properties
Def. Properties that occur when solute particles disrupt the behavior of solvent particles (this disruption is purely physicalthe particles get in each others way.. NOT the attractive interaction that occurs when discussing intermolecular forces) An analogyif it helps you, great! If its confusing, ditch it i.e. if people were solute and solvent particles, an interaction resulting in a colligative property would be like a person who gets in your way as youre trying to move from pt A to pt B. imagine how hard it is to get to the board from your seat when people are in your way very different from an intermolecular force (IMF), which could be represented by someone grabbing hold of you or glomming onto you to make your passage from pt A to pt B difficult. IMPORTANT THINGS TO REMEMBER ABOUT COLLIGATIVE PROPERTIES are the properties of SOLUTIONS, not pure substances!!!! are dependent on SOLVENT identity (how the solvent molecules respond to the presence of solute) are dependent on QUANTITY of solute (the only reason you care if a solute is ionic or not is because ionic compounds dissociate into more particles (the vant Hoff factor, i) The Vant Hoff factor, i = number of particles result from one particle of solvent the maximum value for i can be determined by looking at the formula and type of compound o Most molecular compounds do not ionize or dissociate, so 1 particle of solute only gives 1 particle (vant Hoff factor = 1) ex. C6H12O6, glucose, vant Hoff factor = 1 Acids ionize (strong acids completely ionize; weak acids only partiallymeaning only some percentage of all molecules break apart, so 1 particle of solute give between 1 and 2 particles depending on the acid (1 < vant Hoff factor <2) ex. HCl , vant Hoff factor = 2 ex. HC2H3O2 could be 1.3 (depend on initial concentration and degree of ionization) Soluble ionic compounds ionize; insoluble compounds do not (they act like a molecular compound) ex. CaCl2, vant Hoff factor = 3 (soluble compound, ionizes into Ca+2 and 2 Cl- ions, 3 particles) ex. CaCO3, vant Hoff factor = 1 (insoluble compound)

1. VAPOR PRESSURE (Pvap)LOWERING

Vapor pressure (defined) the equilibrium pressure above a liquid when it is placed in a closed container (where equilibrium can be established)this is an intensive property that does not change with the amount of liquid; it can be looked up in reference books (given the liquid and temperature); -vapor pressure does change with temperature; more intermolecular forces are broken, and the equilibrium pressure is higher. Liquid X Gas X H = + (endothermic process) Kp = Pvapor

-solutes reduce the rate of vaporization i.e. get in the way of solvent molecules getting to the surface and becoming gas molecules, producing a lower vapor pressure Raoults Law The vapor pressure of the volatile solvent in the solution = mole fraction of the solvent x the vapor pressure of the the PURE solvent

Pvap (of the solvent in solution)

XSOLVENT

Pvap (of the PURE solvent)

Note: XSOLVENT = nSOLVENT / (nSOLVENT + nSOLUTE i). Dont forget the vant Hoff factor in the denominator Assumptions o Solute is nonvolatile (doesnt turn into a gas) o This is an ideal solution where concentration is low and solute/ solvent have similar sizes and similar IMFs (i.e. the solute-solvent; solvent-solvent; solute-solute IMF are all roughly the same) if solute-solvent IMF are stronger than average, Pvap is LOWER than predicted (ex. the vapor pressure for some aqueous salt solutions is lower than predicted because of the ion-dipole interaction that occur between the ions and water) if solute-solvent IMF are weaker than average, Pvap is higher than predicted

2. BOILING PT ELEVATION
Boiling pt (defined) the temperature at which the vapor pressure is equal to the pressure above the liquid, usually atmospheric pressure; the temperature at which there is an equilibrium between liquid and gas phases; the temperature at which a liquid boils (liquid gas) How do we get something to boil? Typically the vapor pressure of a liquid is much lower than the pressure above the liquid. So, there are two ways to get something to boil: o o Increase the temperature of the liquid. This shifts the equilibrium forward toward production of more gas, resulting in higher Pvap (same as Kp). When Pvap = Patm, the liquid starts to boil Decrease the pressure above the liquid (create a vacuum). This lowers the Patm so that Pvap = Patm, and the liquid starts to boil

-solutes decrease Pvap; since Pvap is lower, a higher temperature is needed to make Pvap = Patm and the boiling point INCREASES Change in boiling point temperature = Boiling pt elevation constant x molality of particles (for solvent)

Tb

= Kbi m

3. FREEZING PT DEPRESSION
Freezing pt (defined) the temperature at which the intermolecular forces between particles become strong enough to make a liquid into a solid -solutes must be ejected for a solvent particle to form intermolecular forces with another solvent particles; because of the solute particles presence, the temperature at which this occurs must be lower and the freezing point DECREASES Change in freezing point temperature = Freezing pt elevation constant x molality of particles (for solvent)

Tf

= Kfi m

Note: Because solute is ejected, the remaining solution is more concentrated and the freezing point of a solution continually decreases; that is why the freezing point line in the graph below slopes downward

pure liquid (straight)

solution (sloped downward)

Gases
Pressure: Temperature 1 atm = 760 mm Hg of torr = 101.325 kPa = 101325 Pa Kelvin = 0C + 273

MEASURING PRESSURE:

We use manometers or tubes to measure pressure by measuring the pressure of the substance we want to measure (either a gas sample or sometimes the atmosphere) against the pressure of a substance that we know (either by using the atmospheric pressurewhich has already been determined previously with a barometer, or by using a vacuumwhich has a pressure of zero). REMEMBER pressure = push associated with molecular collisions. A higher pressure means it pushes MORE. OPEN-END MANOMETERS A: B:

Pgas = Patm Pgas > Patm Pgas = Patm + h Pgas < Patm Pgas = Patm - h

C:

1)

2)

3) Here, the Pgas > Patm 3) Pgas = Patm + h

Closed-end, one end is a vacuum, which has a P= 0, so. 1)

Pgas = h

2 ) Patm = h

IDEAL GAS LAW & DERIVATIONS: PV=nRT

Avogadros law n1/V1 = n2/ V2

R = 0.0821 L atm mol-1 K-1

(if the pressure and temperature remain constant, the number of moles and the volume of a gas are directly proportional ex. if 0.2 moles takes up 5 L then 0.4 moles would take up 10 L) (if the number of moles and temperature remain constant, the pressure and the volume of a gas are inversely proportional ex. if a gas that takes up 10 L has a pressure of 4 atm is compressed to 5 L, the new pressure will be atm) WHY? When volume is decreased, the number of collisions per unit area on the container increases; therefore the pressure increases.

Boyles law

P1V1 = P2V2

Charles law

V1/T1 = V2/T2

(if the number of moles and the pressure remain constant, the volume and the temperature of the gas are directly proportional ex. if a gas at 300 K that takes up a volume of 20 L is heated to 600 K, the volume will expand to 40 L) WHY? When the temperature is increased, the average kinetic energy of each collision increases and the collisions push the container walls and expand the volume of the container to keep the pressure the same. (if the number of moles and the volume remain constant, the pressure and the temperature of the gas are directly proportional ex. if a gas has a pressure of 2 atm at 200 K, it would have a pressure of 4 atm at 400 K) WHY? When the temperature increases, the average kinetic energy of each collision increases. If the volume is constant, this means that the average force of the collisions per unit area on the container will increases; therefore the pressure increases.

Gay-Lussacs law

P1/T1 = P2/T2

7 Other derivations of Ideal gas law (n=m/MW) and (d=m/V) o To solve for MOLAR CONCENTRATION OF A GAS P = (n/V) RT = MRT (where M= molar concentration)

M=P/RT
o To solve for MOLECULAR WEIGHT OF A GAS PV = (m/MW) RT (where m= sample mass in grams; MW=molecular weight)

MW =(gRT)/ (PV)
o To solve for the DENSITY OF A GAS

P = (m/V) x(RT/MW) = dRT/MW d=(P xMW)/(RT) OTHER GAS LAWS

Daltons law of partial pressures

(where d = density)

PA = XA PTOTAL PTOTAL = PA + PB + PC + .

-often used in problems where a gas is collected over water; PTOTAL (measured) = PDRY GAS + PH2O and the PH2O must be subtracted to get the PDRY GAS. Kinetic energy of a gas KE = (3/2) RT (where R=8.314 J mol-1 K-1) -the kinetic ENERGY of a gas is depend on only the temperature; two gases at the same temperature will have the exact same kinetic energy (because the energy is a related to both the speed AND the mass of a substance, so even though a larger molecule will move more slowly, it has a larger mass) Root mean square (rms) speed of a gas ~ avg speed v= [3RT/MW] (where R=8.314 J mol-1 K-1) -the speed of a gas depends on both the temperature AND the molecular weight; larger molecules move more slowly; smaller molecules move more quickly Grahams Law of Effusion r1/r2 = *MW2/MW1]

IDEAL GASES vs. REAL GASES

VOLUME IDEAL GASES (theoretical, what is predicted by the mathematical formulas) -gas particles are assumed to have no volume INTERMOLECULAR FORCES -gas particles are assumed to have zero intermolecular forces; all collisions are completely elasticthe particles dont stick/ attract to each other -gas particles do have intermolecular forces that cause them to be mildly attracted to each other COMPARISON & CORRECTION VOLUME: VREAL GASES > VIDEAL GASES PRESSURE: PREAL GASES < PIDEAL GASES (P +n2a/V2)(V-nb) = nRT - The PREAL GAS has a correction factor added to it to take the IMFs into account -The VREAL GAS has a correction factor subtracted from it to take the volume of the gases into account

REAL GASES (actual, what is measured in the laboratory)

-gas particles do have a volume and take up space

Gases are most ideal when there are very few intermolecular attractions (HIGH TEMPERATUREmost of the IMFs are broken) Gases are most ideal when they are so far apart that their particle volumes are negligible (LOW PRESSURE)

KINETIC MOLECULAR THEORY

Gas particles have negligible (zero) volume Gas particles move in random, continuous motion Gas particles undergo elastic collisions (no intermolecular attractions, so no sticking) The average speed of a gas particle is directly proportional to the temperature.

Maxwell Boltzmann distribution

Terminology
empirical formula formula with the LOWEST whole # ratios of elements molecular formula the actual formula of the molecule (sometimes the empirical formula and molecular formula are the same) extensive property changes with the amount of substance (ex. heat energy required to melt a substance) intensive property stays constant no matter how much or how little of the substance is present (ex. boiling point or vapor pressure) solvation when solvent molecules surround a solute molecules and dissolve them hydration the process of solvation when the solvent is H2O crystallization the opposite of solvation, where solute particles come out of solution solution a homogeneous mixture of two or more substances solute substance present in lesser quantity in a solution; is dissolved or solvated solvent substance present in greater quantity in a solution; does the dissolving/ solvating dilute not a lot of solute dissolved (qualitative descriptor, no #s!) *Note: a dilute solution can still be saturated if the solute is a fairly insoluble salt concentrated a lot of solute dissolved (qualitative descriptor, no #s!) saturated a solution where solvation and crystallization are in dynamic equilibrium; has as much solute dissolved as it can, will not dissolve more (unless the temperature is changed) Q = Ksp solubility amount of solute dissolved to form the saturated solution (in g/ mL or in Molar the x in ICE) unsaturated will dissolve more solute if added (not at equilibrium) Q < Ksp supersaturated contains more solute dissolved than its supposed to UNSTABLE will precipitate out of solution if disturbed (not at equilibrium) Q > Ksp miscible two liquids that dissolve in each other (ex. vinegar and water); antonym immiscible osmosis when a dilute and concentrated solution are put in contact with each other (via a semipermeable membrane), the net movement of solvent toward a solution of higher solute concentration osmotic pressure the pressure that must be exerted to prevent osmosis when pure solvent is placed in contact with a solution with a given concentration (i.e. the pressure needed to force the solvent particles back/ prevent them from moving toward the concentrated solution)

(where M = molarity of the concentrated solution) colloids - suspensions/ dispersions (type of heterogeneous mixtures that has a uniform consistency, but actually has a non-uniform composition because the solute is not actually dissolved in the solvent, but suspended); colloids disperse light (ex. mayonnaise; milk; lotions) pressure force per unit area; in gases, this is measured by the force provided by gas collisions against a given area of a container or surface temperature a measure of kinetic energy

= (n/V) RT = MRT