1. Section Five Stoichiometric Calculations: The Workhorse of the Analyst

2. Review of Fundamentals Atomic, Molecular, and Formula Weights Moles: 1mole = 6.022 x 10 23 (atoms, molecules or formula units)

3. How Do We Express Concentrations of Solutions? Molarity (M)= moles/liter or mmoles/mL Normality(N) = equivalence/liter or meq/mL Formality(F)= is identical to molarity Molality(m) = moles/1000g solvent

4. In normality calculations, the number of equivalents is the number of moles times the number of reacting units per molecule or atom. ©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

5. Density Calculations How do we convert to Molarity Density = mass solute /unit volume Specific Gravity = D solute /D H20 D H2O = 1.00000 g/mL @ 4 o C D H2O = 0.99821 g/mL @ 20 o C

6. Analytical and Equilibrium Concentrations They are not the same! Analytical Molarity, C x = sum of all species of the substance in solution Equilibrium Molarity, [X] = concentration of a given dissolved form of the substance

7. Dilutions Preparing the Right Concentration The millimoles taken for dilution will be the same as the millimoles in the diluted solution. M stock x mL stock = M diluted x mL diluted

8. Expression of Analytical Results So Many Ways Solid Samples: %(wt/wt) = (wt analyte/wt sample)x 10 2 % pt(wt/wt) = (wt analyte/wt sample)x 10 3 ppt ppm(wt/wt) = (wt analyte/wt sample)x 10 6 ppm ppb(wt/wt) = (wt analyte/wt sample)x 10 9 ppb

9. Expression of Analytical Results So Many Ways Liquid Samples %(wt/vol) = (wt analyte/vol sample mL)x 10 2 % pt(wt/vol) = (wt analyte/vol sample mL)x 10 3 ppt ppm(wt/vol) = (wt analyte/vol sample mL)x 10 6 ppm ppb(wt/vol) = (wt analyte/vol sample,mL)x 10 9 ppb Liquid Analyte %(vol/vol) = (vol analyte/vol sample mL)x 10 2 % pt(vol/vol) = (vol analyte/vol sample mL)x 10 3 ppt ppm(vol/vol) = (vol analyte/vol sample mL)x 10 6 ppm ppb(vol/vol) = (vol analyte/vol sample,mL)x 10 9 ppb

10. The units ppm or ppb are used to express trace concentrations. These are weigh or volume based, rather than mole based. The units ppm or ppb are used to express trace concentrations. These are weigh or volume based, rather than mole based. ©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

11. The equivalents (based on charge) of cations and anions are equal. ©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

12. Reporting Concentrations as Different Chemical Species We may express results in any form of the analyte. Example: Water Hardness due to calcium ion is expressed as ppm CaCO 3. Chloride present in AgCl derived from a salt mixture of NaCl and KCl.

13. Volumetric Analysis - Principles “Titrimetry” – determination of analyte by reaction with measured amount of standard reagent “Standard Solution” (titrant) – reagent of known concentration “Titration” – slow addition of titrant to analyte solution from a volumetric vessel (buret) “Equivalence Point” – reached when amount of added titrant is chemically equivalent to amount of analyte present in the sample. “End Point” – the occurrence of an observable physical change indicating that the equivalence point is reached. Might differ from Eq.Pt.!

14. Volumetric Analysis - Principles How Do We Make Stoichiometric Calculations? Titration- What are the requirements? 1.Reaction must be stoichiometric 2.Reaction should be rapid 3.No side reactions 4.Marked change in some property of the solution when reaction is complete 5.Equivalence point 6.Reaction should be quantitative

15. Volumetric Analysis - Principles Standard Solutions “Primary Standard “ – –highly purified compound used as a reference material in titrimetry Properties: High purity Stable in air Independent of relative humidity Readily available Reasonable solubility Large formula weight

16. Volumetric Analysis - Principles Standard Solutions “Secondary Standard” – do not meet requirements for a primary standard but are available with sufficient purity and properties to be generally acceptable Desirable properties of a Standard Solution: Prepared from primary standard Stable Reacts rapidily and completely with analyte Reacts selectively with analyte

17. Volumetric Analysis - Principles Examples of Standard Materials Primary Potassium Acid Phthalate KHC 8 H 4 O 4 (FW 204.23) Benzoic Acid C 6 H 5 COOH (FW 122.12) Na 2 CO 3, KH(IO 3 ) 2 Arsenious Oxide (As 2 O 3 ) Sodium Oxalate (Na 2 C 2 O 4 ) KI, K 2 Cr 2 O 7, Fe(pure) Secondary NaOH, KOH, Ba(OH) 2 HCl, HNO 3, HClO 4 Sulfamic Acid (HSO 3 NH 2 ) KMnO 4, Na 2 S 2 O 3 Ce(HSO 4 ) 4 (FW 632.6)

18. Volumetric Analysis-Principles Standardization – involves establishing the concentration of a “standard solution” Direct method: dissolve caarefully weighed quantity of primary standard; dilute to known volume Indirect methods: Titrate weighed quantity of primary standard Titrate weighed quantity of secondary standard Titrate measured volume of other standard solution

20. Volumetric Analysis - Principles Acid – Base HA + B  BH + + A - Precipitation M n+ + X -  MX n Oxidation-Reduction Red 1 + Ox 2  Ox 1 + Red 2 Complexation M n+ + Q  M(Q) n+ use standard Q solution

21. Volumetric Analysis - Principles Dilutions V c x C c = V d x C d Stoichiometric Ratios (S.R.) Mole Ratio: What are stoichiometric ratios (mole ratios)? 2 HCl + Ba(OH) 2  2 HOH + Ba 2+ + 2 Cl - 2 MnO 4 - + 5 C 2 O 4 2- + 16 H +  2Mn 2+ + 10 CO 2 + 8 HOH