Definitions: Quantitative Analysis: Process of measuring how much of a constituent is present in a substance.

Systematic Error: Type of error due to procedural or instrumental factors that cause a measurement to be too large or too small (consistent error.) Gaussian Distribution: Theoretical bell shaped distribution of measurements when all error is random. Confidence Interval: Range of values within which there is a specified probability that the true value exists. Analyzed: used for all part of constituents. Substances that are measured are Analytes. Process of measuring analyte is called determination. Indeterminate Errors have an effect on precision. Determinate Errors have an effect on accuracy. Equations: CiVi = CfVf, Gaussian Peak distribution : +-1SD 68%, +-2SD 95%, +-3SD 98%, CI, t = degrees of freedom t90%<t95%<t99% Absolute Error vs. Relative Error: Absolute error is BA(accepted value) and Relative Error is |B-A| /A Calibration/Linear Regression: A1 = bc, =molar absorptivity, b= path length, c=concentration. So how to find Cu? Create a ratio Au/As = Cu/Cs Then get a linear line => y = mx + yintercept. The y is absorpt ion, x is the concentration, and m is the b . The y-intercept is usually some sort of error T-test: Tells you whether there is a statistical difference between numbers. If the t-test calculated is larger, then yes there is a statistical difference. Expressing Concentrations: ppt=(Weight solute/Weight Sample) * 10^3, ppm = (Weight solute/ Weight Sample) * 10^6, ppb=(Weight Solute/ Weight Sample) * 10^9 So in general if you want to calculate wt/vl first get it into g/mL then multiple by 10^6, 10^9, 10^12 Titrations: Equivalence point is where moles of titrant = moles of analyte. The Ve is the point where half of the analyte is neutralized. If Acid Titraion H^+ + OH^- => H2O . The H^+ is the titrant and the OH^- is the unknown. For photometric titration, the signal is usually absorbance. Acid and Bases: Kw/Ka = Kb and [OH-] = sqrt((Kw/Ka) * Ca) , 14 =pH + pOH Buffers: Buffers are the best when pKa += 1 = pH. Ionic Strength: Plotting between f(the activity coefficient) and , M(ionic strength). Ai is the activity of the ion and ai= fi[i] Types of Problem: A. Problems dealing with concentrations: General Formula is A+B => C+D, [C][D] / [A][B] C, and D are always the limiting reagent moles. Set this equation equal to equilibrium constant. Can use to find moles/molarity. B. Problems dealing with Precipitate (finding percent mass) The general equations to follow is grams of total precipitate * (MW of what you want/ MW of precipitate) / grams of whole Sample * 100% C. Problems dealing with finding Molarity of precipitating solution. Break it up. So if precipitation of Ag3PO4 => [Ag^+]^3 [PO4^3-] Using the Ksp, can figure out Molarities. D. Determining Solubility For a case like Ag2CrO4 know this will become => 2Ag^+ + CrO4^2-, so to set up the equtions [Ag]^2 [CrO42^-] = ksp. Know the molarity of the KCrO4^2- solution to be 0.10. So [S]^2[S+.10] = ksp E. Problem dealing with Acids and a known Concentration Example if you know that the hydrogen concentration of a .100 M solution of trichloroacetic acid then HT => H^+ + T^-, so becomes x^2/ .100-x = .129 F. Problems about Buffers. Whenever dealing with a Buffer problem want to use the Henderson-Hasslebalch equation pH = pKa + log[proton acceptor / proton donor] and pka = pkw pkb. So if you have an excess of acid you can use the Henderson-Hasslebalch equation straight away, but if you have more base than first use pka=pkw pkb, to figure out pka then use the Henderson . F. Quantitative Determination from titrations 1. Determine the concentration of the titrant. Ex. If used x grams of Tris and endpoint was x mL of HNO3. Then x grams of Tris * (1mole of Tris/ MW of Tris) * (1 mole of HNO3/ 1 mole of Tris) which gives you moles of HNO3, then can calculate molarity. 2. Determine amount of mls of titrant needed to titrate then x mL of titrant * (Concentration of titrant) * (1mole of Tris/ 1 mole of titrant) * (MW tris/ 1 mole tris) G. Problems with EDTA The formation constant of EDTA is kf = (kf)(H) and 1/H = 1 + [H^+] / ka4 + [H^+)^2/ka4ka3 + [H^+]^3/ka2ka3ka4 + [H^+]^4/ka1ka2ka3ka4. EDTA is also produced from N a2H2Y 2H20 Precipitates: CO3^2-, NO3-, NO2-, SO4^2-, SO3^2-, ClO4^-, HCO3^-, S2O3^2-, HSO4-, HSO3-, PO4^3-, HPO4^2-, H2PO4^-, CN-, OCN-, SCN-, NH4^+, H30^+, Hg2^2+, CrO4^2-, Cr2O7^2-, MnO4^-, OH^-, O2^2-, C2H3O2^- % tolerance of Glassware: Graduated Cylinder- 2%, measuring pipet- 1%, volume pipet-0.2%, buret-0.2% Ppm Wt/wt Wt/vol Vol/vol Mg/kg, Mg/L Ul/L ug/g Ug/ml Nl/ml ppb Ug/kg Ug/L Nl/L Ng/g Ng/ml pL/mL Example problems: 1. Buffer solution is made by mixing 40 mL of .03 M H2SO4 with 50 mL of .08 M NH3( the pKb of NH3 = 4.75) Calculate the pH. 1. Find out the moles of H2SO4 and NH3 used. .04L * .03M = 0.0012 moles of H2SO4, however 1 mole H2SO4 = 2 moles H+ so .0012 * 2 = .0024 moles. Then for NH3, .05 L * .08 M = .004 moles. So because the NH3 is in excess, .004-.0024 = .0016 moles will still be NH3, while .0024 moles will become NH4+. 3. Then using the pka = pkw pkb, we find that the pka is 14-4.75 = 9.25. And then plug into the Henderson-hasslebach equations pH = 9.25 + log(.0016/.0024) 2. Aluminum content is determined by precipitating it with oxine to give Al(C9H6ON3). If 1.021 g sample yielded 0.1862 g of precipitate, what is % Al? g of total precipitate * (MW of what you want/ MW of precipitate) / g of sample. 3. Solubility Product calculations: What must be the concentration of PO4^3- to just start precipitation of Ag3PO4 in a 0.10 M AgNO3 solution. Know that the solubility equation will be [Ag+]^3[PO4^3-] = Ksp, so [s]^3 [.10] =Ksp. 4. What is the solubility of Ag2CrO4 in 0.10 M K2CrO4? Know that Ag2CrO4=> 2Ag+ + CrO4^2-, so solubility is [2s]^2[s+0.10]=Ksp 5. Dilution Calculations: How many mls of .10 M of H2SO4 must be added to 50 mL of 0.10 M NaOH to give a solution that is 0.05 M H2SO4. So .05M(50ml+x) = 50ml(.10M) + x(.10M), solve for x. 6. Weak Acids and Bases: Calculate the Hydrogen ion concentration in a 0.100 M solution of trichloroacetic acid. Know the acid will dissociate like HT => H+ + T-, Start with 0.100M but then after dissection becomes [x][x] / .100-x = .129 7. Salts of weak acids and bases: Calculate the pH of the solution obtained by adding 20 mL of 0.10 M HOAc to 20 mL of 0.10 M NaOH 2 equations to use Kw/Ka = Kb and [OH-] = sqrt(Kw/Ka * Ca) So we know the Ka of acetic acid which is 1.75E-5, and we know that Kw is 1*10^-14, so we need to find the concentration of the acid Which is .10M * 20 ml = 2 mmol, then 2 mml/(total of 40ml) = .050 M in the final solution. So then can solve for concentration of OH-, allowing you to get pOH which is the Log of OH-. 8. Buffer Solution: Buffer solution is prepared by adding 20 mL of .10 M sodium hydroxide solution to 50 mL of .10 M acetic acid solution. What is pH of buffer? In this situation there is an excess of the acid. pKa of acetic acid is 4.76. .02 * .10 M is equal to .002 moles of NaOH, and then .005 moles of the acetic acid. NaOH is limiting reagent, so there will be .003 moles left over. So pH =4.76 + log(.002/.003) 9. Buffer problem, where there is an excess of the base. Buffer solution is prepared by adding 25 mL of .050 M sulfuric acid to 50 mL of .10 ammonia solution. What is the pH of the buffer? So 1.25 mmols=> however, each mole of sulfuric acid produces 2 moles of H+, so 2.50 moles of the sulfuric acid and then 5 mmols of the ammonia solution. So pKa = pKw-pKb, so pKa = 14-4.76(the pKb is given for the ammonia solution) then pH = 9.24 + log(NH3/NH4+) => ph= 9.24 + log(2.50/2.50) 10. Titration, standardization calculation. Sodium hydroxide solution is standardized by titrating .8592 g of primar standard potassium acid phthalate to a phenolphthalein end point, requiring 32.67 mL. What is the molarity of the base solution? 859.2 mg / 204.23 mg/mml / 32.67 mL will equal the concentration. 11. Quantitative determination of titrations, .492 g sample of KH2PO4 is titrated with 0.112 M NaOH, requiring 25.6 mL, percent purity? .112 mmoles/ mL * 25.6 mL * 1 mole KH2PO4/ 1 mole NaOH * 136 mg/ 1mmol KH2PO4 which is equal to 389.9392 mg of KH2PO4, then .3899392g/.492 g *100 will give you percent purity. 12. EDTA titration problems, standard solutions. An EDTA solution is standardized again CaCO3, by dissolving .3982 g CaCO3 in HCL acid and adjusting the pH to 10. If 38.26 ml required for titration the molarity of EDTA? Assume that 1 mole of EDTA reacts with 1 mole of CaCO3. So the M of EDTA * 38.26 ml = .3982 g / MW of CaCO3