CHEM 105B LAB STUDY GUIDE Laboratory Techniques Precision of Measuring Instruments Thermometer 10 ml graduated cylinder 50 ml graduated cylinder

Analytical balance Buret Mohr Pipets Weighing by Difference, Tare Function Read the meniscus from the bottom (eye level) Proper use of a graduated pipet rinse entire pipet wetting the inner surface (2x water, 1x new solution) dilution=volumetric flask Erlenmeyer flask/beaker/pipet - dry or rinsed twice with solution being used bunsen burner - flame about two inches from stand use wire gauze under beaker penny head stopper bottles - never put stoppers on the lab bench mixing solutions in test tubes holding the test tube at the top and lightly tapping the side universal pH indicator - transfer clean drop red=2 orange=4 yellow=6 green=8 blue=10 centrifuge - always monitor, always have 2 or 4 test tubes at a time pH meters - must be calibrated acidic - ph 7 then ph 4 basic - ph 10 then ph 7 must always be stored in the proper buffer solution, fill cap with storage buffer spectrometer light travels through the long side of the cuvette calibrate with a reference cuvette fill cuvette 3/4 with sample Error Analysis

Experiment 1: Reaction Kinetics: determining the Rate Law THEORY: reaction rates allow one to predict the OBSERVED INITIAL RATE in terms of the INITIAL CONCENTRATION of THE REACTANTS if aA + bB --> cC, then rate=[A]n[B]m k is temperature-dependent and is the primary determinant of a reactions speed overall order=n+m must be determined experimentally because may not equal coefficients a and b rate =(-1/a)(d[a]/dt)=(-1/b)(d[b]/dt)=(1/c)(d[c]/dt)= [A]n[B]m assume A --> products, then rate = (-1/a)(d[a]/dt) = k[A]x zero order: x=0, [A]t= -kt+[A]0 first order: x=1, ln[A]t= -kt+ln[A]0 second order: x=2, 1/[A]t= -kt+1/[A]0 y=mx+b depending on the order of the reaction, only one of the above will yield a linear plot zero order, first order --> slope=-k, second order --> slope=+k reaction between crystal violet and sodium hydroxide CV+(aq) + OH- (aq) --> CVOH (aq) rate=k[CV+]n[OH-]m rate law integrated form is only described for the simplified reaction of A -->products large excess of NaOH used --> pseudo n order reaction rate=k[CV+]n k=k[OH-]m Measure absorbance to detect the concentration of the crystal violet as the absorbance decreases, more crystal violet has been used record absorbance as a function of time and then determine which order has a linear relationship between time and concentration of crystal violet A=E x l x C the plots will yield k. From there, the different trials using different high concentrations of OH- will allow a plot of [OH-] vs. k. The slope of the linear plot will give the k value. PROCEDURE: run 4 trials of CV and NaOH mixtures with total volumes of 10 ml

 all 4 trials should have the same volume of the initial CV stock solution different volumes (but relatively large concentrations) of NaOH immediately after mixing well in the volumetric flask, pour sample into cuvet and record absorbance over time Experiment 2: The Law of Mass Action: Le Chatelier's principle THEORY: Le Chatelier's Principle - If stress is imposed on a system at equilibrium, the equilibrium concentration of reactants and products will shift in such a manner as to relieve the stress equilibrium constant for a chemical reaction is compared to a perfectly balanced seesaw heat consume (endothermic) = reactant heat produced/evolved (exothermic) = product distinguishable colors allow the relative amounts to be seen easily for acid-base reactions, the extent of reaction can be judged visually by the color of an appropriate acid-base indicator presence of a solid product in a precipitation reaction provides another simple visual indication of reaction progress PROCEDURE: Reaction #1: CrO42- <--> Cr2O72 yellow <--> orange Reaction #2: HIn + H2O <--> In- + H3O+ orange <--> red-pink Reaction #3: [CoCl4]2- + 6H2O <--> [Co(H2O)6]2+ +4Cl blue <--> pink Reaction #4: [Cu(H2O)4]2+ + 4NH3 <--> [Cu(NH3)4] + 4H2O Reaction #5: CaCO3(s) <--> Ca2+ + CO32 Reaction #6: NH4Cl (s) <--> NH4+(aq) + Cl- (aq) Reaction #7: Zn2+ + 2OH- <--> Zn(OH)2(s) ; Zn(OH)2(s) +2OH- <--> Zn(OH)42 Reaction #8: ???? Reaction #9: ???? Experiment 3: Acid-Base Equilibrium: Exploration of Buffers THEORY: finding the dissociation constant, Ka, is found by measuring the pH of several buffer solutions in which the total amount of undissociated acid and conjugate base is kept constant but the ratio of base to acid changes use Henderson-Hasselbalch equation to determine dissociation constant

 pH=pKa + log[A-]/[HA] the greater the value of Ka, the greater the degree of dissociation pH sensor is an example of a galvanic cell whose output voltage is proportional to the difference between the concentration of hydrogen ion in the test solution and the concentration of hydrogen ions that are contained in reference cell located in the body of the sensor a good working buffer solution is one that is able to resist changes in pH despite the addition of small amounts of additional acid or base buffer solutions will be prepared by partially neutralizing a weak acid solution with a strong base adding different quantities of a known NaOH solution to several samples of the original unknown acid solution to give solutions with various ratios of acid to conjugate base acid-base reactions involving a strong base fo to completion, that is, the reaction proceeds until one reactant is exhuasted all acid-base buffer and titration calculations start as limiting reactant problems PROCEDURE: four different solutions, all have the same volume of unknown weak acid, varying volumes of 1.0 M NaOH volume of de-ionized water corresponds with volume of NaOH so that all four solutions have the same total volume test for the pH of each solution after they have been thoroughly mixed the pH meter should be immersed about an inch into the solution for each solution calculate the pKa using the Henderson-Hasselbach equation ratio of conjugate base to weak acid is calculated from the stoichiometry of the neutralization reaction using the exact volumes and concentrations of the solutions that you have recorded in your data table. Experiment 4: Acid-Base Equilibrium: Potentiometric Titration of Weak Acids THEORY: during a titration, a prid quantitative chemical reaction takes place between the substance being analyzed (in this experiment, an acid solution) and the titrant (NaOH solution in this experiment) the equivalence point - the point in titration at which stoichiometrically equivalent quantities of acid and base are present

 equivalence point can be detected by using an acid-base indicator, or by interpreting graphs made by plotting the different pH values as the standard NaOH is added to a fixed quantity of the acid being analyzed pH meter is a high impedence voltmeter that measures the voltage (potential) of a voltaic cell, allows the passage of a negligible amount of current, so that the chemistry of the system is not disturbed one of the half-reactions in the cell has a potential that varies as a function of H+ concentration the other half-cell has a fixed potential, this is the reference electrode the other electrode responds to change in H ion concentration when a thin conducting glass membrane is placed between two solutions with different H ion concentration, a minute but measurable voltage develops across the membrane the reference and glass electrode are commonly packaged together in a combination electrode which appears to be a single electrode, but which contains two will find the equivalnce point graphically from a plot of the pH that you will measure versus the volume of the strong base titrant determine pKa for the acid monoprotic acid 1/2 equivalence point when pH=pKa buffer region inflection point, equivalence point, equivalence point within the buffer region, relatively large additions of titrant cause relatively small changes in pH within the buffer region, point of lowest slope, 1/2 equivalence point, where the volume=1/2 of the equivalence volume near the equivalence point, very small additions of titrant cause large changes in the pH polyprotic acids see these superposition of the monoprotic curves dissociate stepwise pKa2 and pKa3 are not resolvable for some weak acids and only pKa2 can be discerned by this method PROCEDURE: titration must be done very slowly about 40 mL of acetic acid into a clean dry 250 mL Erlenmeyer flask make sure the exact amount added is recorded measure intial pH titration with 0.35 M NaOH, measure after each addition of NaOH

add 1 mL in 0.2 mL aliquots add the next 10-13 mL in 1.0 mL increments add the next 1 mL in 0.05 ml increments alternate between different size aliquots depending on the jumps in pH between previous measurements if pH jumps by 0.3 of more, decrease the size of the aliquot if pH increase by less than 0.3, maintain or increase aliquot size data analysis: graph of pH vs mL of base added; graph of 1/delta pH vs volume OH- added (Gran plot) three ways to find pH initial pH and the calculated molarity of the acetic acid solution pH value halfway to the equivalence point pH at the equivalence point and the concentration of sodium acetate formed Experiment 5: Acid-Base Equilibrium: The Spectrophotometric Determination of pKa THEORY: dilute aqueous solutions containing light absorbing solutes obey Beers Law and the concentration of the solute in a solution can be determined from the measurement of the absorbance at a suitable wavelength having previously determined the molar absorptivity Beers Law: A=ElC the object of the experiment is to determine the dissociation constant for a weak acid using particular circumstance that the undissociated acid, HIn, has one color, and the anion In-, has a different color in this experiment, thymol blue is the acid-base indicator determine the concentrations of HIn and In- spectroscopically solving for two unknowns because both series are absorbing light according to Beers Law, the total absorbance at any one wavelength of a solution containing HIn and In- will be given by: Atotal= EHInl[HIn] + EIn-l[In-] determine the wavelength of maximum absorption for both thymol blue and its dissociated form determine the molar absorptivity of each form of thymol blue at each lamba max determine the pKa of the weak acid thymol blue by spectroscopically determining the concentrations of the dissociated and undissociated

forms, at four different pH values PROCEDURE: make a highly acidic solution (solution #1: 1 mL HIn and pH 5 buffer solution) make a highly basic solution (solution #2; 1 mL HIn and 1.0 ml NaOH solution and then dilute to mark with deionized water) obtain solutions #1 and #2 absorption spectrum determine lamba max of each solution, record absorbance at these points record lamba max of Solution #1 at lamba max of Solution #2 and vice versa use this value and the concentrations to determine the E of each species prepare four more solutions with 1.0 mL of HIn, and then filled to the ark with buffers 1-4 record the pH of each solution and the absorbance at each of the two wavelengths previously determined as solutions #1 and #2 lamba max solve algebraically using two of any of the solutions prepared with buffers 1-4 our statement of mass balance would be reversed as an insurance against catastrophes Ctotal=[HIn] + [In-] if one of the values for [HIn] or [In-] is unrealistic, then use the above equation to obtain a more reasonable value use these values in the Henderson-Hasselbach equation plot of log [A1buffer-A1solution#2]/[A1solution#1-A1buffer] vs pH give a line with a slope of -1 and an x-intercept equal to the pKa Experiment 6: Application of Equilibrium: Qualitative Analysis - Group I Cations THEORY: qualitative analysis scheme, large mixture of ions can be separated into a small number of groups and then each ion within the group can be individually separately and identified the separation and identification schemes rely heavily on the application of solubility and complexation equilibria. the separation of the initial mixture into a few subgroups takes advantage of the pH dependence of the solubilities of chlorides and sulfides as shown in the following flowchart PROCEDURE:

Experiment 7: Application of Equilibrium: Qualitative Analysis - Group III Cations THEORY: PROCEDURE: Experiment 8-I: Electrochemistry: Galvanic Cells THEORY: electrochemistry is concenred with the relationship between chemical and electrical energy chemical energy <--> electrical energy in a galvanic cell, a pair of electrochemical half-reactions (oxidation and reduction half-reaction) are physically separated and electrically coupled through an external circuit so that the flow of e- through the circuit can be harnessed to produce useful electrical energy need to consider the buildup of negative charge and positive charge when electrons travel from the anode to the cathode solution:salt-bridge containing high concentration of an unreactive electrolyte such as KNO3 (a low resistance solution) connects the two solutions to allowt he flow of ions to maintain charge neutrality while impeding the flow of the silver ions which would short-circuit the cell anode (left); salt bridge; cathode (right) |=phase boundary ||=salt bridge anode=site of oxidation cathode=site of reduction every half-cell needs an electrically conducting solid electrode to physically connect the half-cell reaction to the eletrical circuit the electrode does not need to be invovled in the elctrochemical reaction if the half-cell reaction does not have a solid, conducting reactant or product to act as the electrode, a passive electrode (Pt, graphite) must be used overall cell reaction = reduction half reaction + oxidation half reaction arbitrarily assign the half reaction of H+ and e --> H2a value of 0.0V all half reactions can then be assigned half reaction potentials using this reference system. reverse the reduction potential of the half-cell that is being oxidized Ered+Eox=Ered-Eox

PROCEDURE: Experiment 9: Transition Metal Coordination Compounds: Applications of Crystal Field Theory THEORY: the change in color of the different complexes as an indication of the position of the equilibrium the color of the complexes is due to the absorption of photons with energies in the visible range of the electromagnetic spectrum the energy of light absorbed is correlated to the difference in energy between the group state electronic state and the excited electronic state careful analysis of absorption and emission spectra give information about the electronic configurations of atoms and molecules ligands around a transition metal are considered to be negative-point charges arranged in aspecficed geometry around the central transition metal ion the presence of the negative point-charge ligands causes repulsive interaction with the d-orbitals of the central metal ion the degeneracy of the five d-orbitals is removed and the relative energy levels of the d-orbitals can be rearranged in a predictable manner by considering the geometry of the arrangement of the ligands and the orientation of the d-orbitals no ligands = all 5 d-orbitals of metal ion are degenerate spherical field of negative charge around metal ion = all 5 d-orbitals remain dependerate but increase in energy due to repulsive interactions octahedral arrangement of 6 ligands around metal ion=2 are higher energy than 3 other d-orbitals PROCEDURE: prepare different solutions, measure their absorption spectra wavelength of max absorption indicate energy absorbed by the series smaller wavelength, higher energy and vice versa Experiment 10: Introduction of Organic Chemistry Experiments - Extraction of Caffeine THEORY: the extraction of a solute from a solution and the separation of a solute from a solvent by evaporation of the solvent liquid-liquid extraction PROCEDURE: