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West Virginia University Strong and Weak Acids Questions

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1. Discuss any three interactions that happen in water. Provide the reaction, what’s happening, why, and what parameters influence those reactions . 2. Define the following terms. Provide a sketch . Vadose Zone: Water Table: Saturated Zone: Impermeable Layer; Total Dissolved solids: 3. Identify the acid and the base in this reaction : HCO3- = H+ + CO32- 4. This graph illustrates the relationship of pH (bottom) and CaCO3 (calcite, top) solubility as a function of PCO2. This figure assumes that our beaker includes water, CO2 and calcite. A vertical line has been added at the location of atmospheric background for CO2. Based on this figure, answer the following questions for this system. a. What is the approximate pH of water in equilibrium with atmospheric CO2 concentrations? b. For a solution in equilibrium with 80 mg/L of CaCO3, what must the PCO2 be? c. For a solution in equilibrium with 80 mg/L of CaCO3, what must the pH be? d. Where on the graph would a solution be (a) in equilibrium with calcite, (b) supersaturated with respect to calcite, and (c) undersaturated with respect to calcite? You can answer in words or illustrate your answer on the upper figure half of the figure above. e. If you were looking at a solution with ONLY CO2 and water (that is, no calcite), would the pH be higher or lower than predicted here? Explain your answer. 5. Sketch the Carbonate Bjerrum plot with pKa’s and describe what’s happening on the graph with respect to species concentration and pH . 6. What are 4 tools or equations we can use to analyze karst waters/systems? What do these tools/equations tell us? 7. What are 6 ways that acid-base and redox-chemistry differ? Be specific (for example, don’t say “they are different by temperature” tell me something like redox reactions happen at high temperatures and acid-base happen at low temperatures”1). 8. Why does pyrite weather (oxidize) when coal mining takes place? 9. Balance the following redox reaction. Pease show all half reactions, the full reactions, and which species are being oxidized and reduced. 𝐶𝐻2 𝑂 + 𝑂2 −→ 𝐶𝑂2 + 𝐻2 𝑂 10. We talked about terminal electron acceptors. How do those get incorporated into the breakdown of organic C? 11. What is the driving source of climate change? What are selective absorbers and what do they do? 12. What are 3 examples of climate proxies and how do we use them to understand past and current climate? Species Ca2+ Mg2+ HCO3 pH (H+) = 7.5 Mg/L 50 20 250 – Mol. Weight 40.1 24.3 61 1 Z (charge) 2 2 1 1 Mol/L 1.25E-3 8.23E-4 4.1E-3 10^-7.5 Ionic strength = measure of conc. Of all ion in a soln 𝐼𝑆 = 1 Σ[i]𝑧2𝑖 2 i = mol/L of each ion in soln; z = charge IS = ½ x ([Ca]22 +[Mg]22 + [HCO3]12 + [H+]12) = 4.12E-3 Hardness • Controlled by divalent cations, Mg and C • Measure in mg/L CaCO3 (calcite, or limestone) Hardness = 50,000 ([𝐶𝑎]𝑧!” + [𝑀𝑔]𝑧#$ ) à molar concentrations of Ca, Mg 50,000? = conversion factor for CaCO3 For the data above = 207 mg/L Ca/Mg Molar Ratio Ca/Mg (mol/L) = units cancel, unitless CaCO3 à Ca2+ + CO32molar ratio >>>>> 1 calcite, in real life likely some Mg impurities; CaMg(CO3)2 à Ca2+ + Mg2+ + CO32- dolomite,~ equal amt of Ca and Mg; molar ratio ~ 1 PCO2 CO2(g) + H2O à H2CO3* H2CO3* à + H + HCO3- 𝐾%&!’ 𝐾- = [*! %&”∗ ] ,$%! [* & ][*%&”‘ ] [*! %&”∗ ] Calculating Pco2: Step 1. • Solve the KCO2 equation for PCO2 𝐾%&!’ [*! %&”∗ ] ,$%! = 𝑃%&! = [*! %&”∗ ] .$%! a Step 2. • Solve K1 equation for H2CO3* 𝐾- = [* &][*%&”‘ ] [*! %&”∗ ] Step 3. • Sub b into a = [𝐻/ 𝐶𝑂0∗ ] = [* & ][*%&”‘ ] .) b [𝐻2 ][𝐻𝐶𝑂03 ] [𝐻/ 𝐶𝑂0∗ ] 𝑃%&! = = = 𝑃%&! 𝐾%&! 𝐾- 𝐾%&/ This is often reported in logPCO2 K1 and KCO2 are tabulated for different temperatures, you can look these up in tables REDOX CHEMISTRY • Redox = oxidation chemistry • It’s the movement of e-s • Generates an ELECTRICAL GRADIENT • Sometimes “electrochemistry’ • 2 major steps o 1. Oxidation, loss of e-s o 2. Reduction, gain of e-s = in terms of charge; REDUCING CHARGE, must gain e-s Example of Oxidation: Example of Reduction: 𝐹𝑒 /2 −→ 𝐹𝑒 02 + 1𝑒 3 𝐶𝑜02 + 1𝑒 3 −→ 𝐶𝑜/2 IMPORTANT: The above are half reactions, meaning they ALWAYS occur together in pairs (oxidation AND reduction). You cannot have one without the other. The Whole reaction for the example: 𝐹𝑒 /2 −→ 𝐹𝑒 02 + 1𝑒 3 𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 + 𝐶𝑜02 + 1𝑒 3 −→ 𝐶𝑜/2 𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 = 𝐹𝑒 /2 + 𝐶𝑜02 + 1𝑒 3 −→ 𝐹𝑒 02 + 1𝑒 3 + 𝐶𝑜/2 = 𝐹𝑒 /2 + 𝐶𝑜02 → 𝐹𝑒 02 + 𝐶𝑜/2 𝑊ℎ𝑜𝑙𝑒 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 In whole rxns, there’s AT LEAST 1 oxidized and 1 reduced species; e-s cancel out and are not written Determine Oxidation State for different species – Rules of Thumb 1. Are there neutral species? à sum of all elements oxidation = 0 2. Ionic species à sum of all elements oxidation state = charge on the ion 3. Elemental species à oxidation = 0 (ALWAYS) Others: Descriptor 4. Group 1 on P-Table 5. Group 2 on P-Table 6. Oxygen 7. Hydrogen 8. Fluoride (Fl) 9. Chloride (Cl) 10. Transition metals Oxidation State 1 (Na+, K+) 2 (Ca2+, Mg2+) -2 (usually); exceptions = O2, peroxides, organics = 0 +1; exception H2 = 0; hydrides = +1 -1 -1; Cl2 (chlorine gas); and some oxygenated compounds Variable OIL RIG = Oxidized Is Losing; Reduction Is Gaining (wrt to e-s) LEO GER = Losing Electrons Oxidizing; Gaining Electrons Reduction Balancing Redox Reactions 1. Determine the oxidation state of all elements of interest 2. Identify which elements are changing state and which are oxidizing and which are reducing 3. For half reactions: a. Write skeletal reaction (oxidation half or reduction half) b. Add e-s were needed (to balance charge) c. Balance O H2O – don’t use O2 because you’ll introduce a different oxidation state; more complicated d. Balance H using H+ 4. Combine half reactions. May need to multiply through to cancel es 5. Cancel any redundant species 6. Final check charge and species balance Example: Organic C combustion/consumption 𝐶𝐻/ 𝑂 + 𝑂/ −→ 𝐶𝑂/ + 𝐻/ 𝑂 Oxidation state = blue Oxidation = red Reduction = green 1. Determine oxidation 2. See what’s changing +1 C is being oxidized (lose e-, become more positive) +4 -2 𝐶𝐻/ 𝑂 + 𝑂/ −→ 𝐶𝑂/ + 𝐻/ 𝑂 0 -2 -2 0 +1 O is being reduce (gain e-, become more negative) 3. Half reactions: Oxidation Half: + Reduction Half: 4. Combine 5. Cancel 𝐻/ 𝑂 + 𝐶𝐻/ 𝑂 = 𝐶𝑂/ + 4𝑒 3 + 4𝐻2 4𝐻2 + 4𝑒 3 + 𝑂/ → 2𝐻/ 𝑂 = 𝐻/ 𝑂 + 𝐶𝐻/ 𝑂+ 4𝐻2 + 4𝑒 3 + 𝑂/ = 𝐶𝑂/ + 4𝑒 3 + 4𝐻2 + 𝑂/ → 2𝐻/ 𝑂 = 𝐶𝐻/ 𝑂 + 𝑂/ −→ 𝐶𝑂/ + 𝐻/ 𝑂 𝑤ℎ𝑜𝑙𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 Strong and Weak Acids, pKa pKa = -log(Ka); quantitative measure of strength of the acid Ka = dissociation constant of the acid; the equilibrium constant of each H+ dissociation reaction Lots of acids have more than 1; that is there is a Ka for every H+ that can be dissociated from the acid Strong Acids pKa Weak Acids -4 -2 0 2 4 6 8 10 104 102 100 10-2 10-4 10-6 10-8 10-10 Ka 12 10-12 𝐶𝑂! + 𝐻!𝑂 = 𝐻!𝐶𝑂”∗ 𝐾$%! [𝐻!𝐶𝑂”∗] = 𝑃$%! 𝑙𝑜𝑔𝐾$%! = −1.47 pKa -4 -2 0 2 4 6 8 10 104 102 100 10-2 10-4 10-6 10-8 10-10 Ka 𝐻!𝐶𝑂”∗ = 𝐻& + 𝐻𝐶𝑂”‘ 𝐻& [𝐻𝐶𝑂”‘] 𝐾( = [𝐻!𝐶𝑂”∗] 𝐾!”# 𝐾# 𝐾$ DIC = CO2 (gas) + H2CO3 + HCO3 + CO3 𝑙𝑜𝑔𝐾( = −6.35 𝐻𝐶𝑂”‘ = 𝐻& + 𝐶𝑂”!’ 𝐻& [𝐶𝑂”!’] 𝐾! = [𝐻𝐶𝑂”‘] 𝑙𝑜𝑔𝐾! = −10.33 pH = 6.35 pH = 10.33 12 10-12 Saturation indices – various minerals, esp. calcite & dolomite Mg/L CaCO3 0-60 Soft 61-120moderately soft 121-180 hard >180 very hard æa a ö SI C = logçç Ca CO3 ÷÷ è KC ø 2 æ a Ca a Mg a CO 3 SI D = logç ç KD è What might we monitor? Field measurements Temperature pH (wait for redox!!) Alkalinity Specific conductance (ionic strength) Lab Analyses Ca Mg Derived Parameters Hardness Ca/Mg molar ratio PCO2 SIc SId ö ÷ ÷ ø CO2 pressures in soils Magotes Ý Cockpit karst PR Þ Mendip Hills UK Tytoona Arch-Spring Cave System Arch Spring Sinkhole spring SINK HOLE OPEN CAVE Near sump Fully submerged system Terminal sump SINK HOLE cre ek Cave entrance OPEN CAVE The arch from downstream From on top of the arch, looking upstream to the spring opening #4 #2 Troester and White (1984) Tytoona cave system #4 #3 #2 #1 #3 #4 #3 #2 #1 Linking spring water chemistry to flow systems Shuster & White (1971). Central PA Spruce Creek Spring & Birmingham Cave Spring Rock Spring Spruce Creek Spring & Birmingham Cave Spring Rock Spring Spruce Creek Spring & Birmingham Cave Spring Rock Spring Birmingham Cave Spr Rock Spring Degassing & Precipitation Rimstone Dams Lorah and Herman (1988). Falling Spring Creek, VA Lorah and Herman (1988). Falling Spring Creek, VA Waterfalls & Tufa deposition in Allegheny County VA Waterfalls & Tufa deposition in Allegheny County VA (Johnathan Moore) Tufa & travertine deposition in Croatia Plitvice Lakes National Park, Croatia (UNESCO World Heritage Site) Using chemographs over shorter time periods == STORM SAMPLES Dreiss (1982 – 1984) Meramec Spring MO Dreiss, Missouri springs Storm Samples Fort Campbell (Vesper & White, 2003) Understanding PCO2 v SI(calcite). Why do tropical springs precipitate calcite more readily than temperate springs with the same SIc? White (1997) Biogeochemical cycles & carbonate geochemistry DIEL CYCLES De Montety et al. (2011) Influence of diel biogeochemical cycles on carbonate equilibrium in a karst river. Chemical Geology 283: 31–43. Biogeochemical cycles & carbonate geochemistry Monitoring with loggers Austin Blind Salamander ­ Barton Springs Salamander ® https://www.caudata.or g/cc/species/Eurycea/E_ sosorum.shtml Barton Springs data, Mahler & Bourgeais (2013) Water Quality as a tracer of source area Ryan, M., J., 1996. An examination of short-term variations in water quality in a karst spring in Kentucky. Ground Water, 34(1): 23-30. Mixing Corrosion & Flank Margin Caves WHERE IS THE WATER? % of total RESERVOIRS 0..001% % of terrestrial reservoirs 2% 72% 0.15% 5% 0.6% 23% 97% WHAT’S IN THE WATER? Interactions that take place in water • Minerals dissolution and precipitation • Minerals weather (incongruently) to form new minerals • Reactions IN solution – between dissolved species, between solids & dissolved species, • Through this process….. water acquires more and more “stuff” = TDS (total dissolved solids) • How much stuff? Depends on o Rock types present o Duration of the interaction (flow through time, contact time) o Climate (rainy areas dilute, arid regions evaporate) SOME IMPORTANT TERMS Vadose zone: also called the unsaturated zone; between the land surface and the water table; pores only partially filled with water Water table: top of the zone of the saturated zone; pores fully saturated; pressure head = atmospheric head Saturated zone: aka phreatic zone; all pores filled with water Impermeable layer: confining layer or aquitard; layer of rock; usually a very compact rock with little pores (shales, quartzite, among others Total dissolved solids (TDS): measure of all dissolved components in water; organic, inorganic, molecular, ionized, colloids; measured in parts per million (ppm) THINKING ABOUT TDS What’s the pH in rainfall? How does it change once rocks start to weather? Where is Ca the highest? Why? Why such a difference bewtween tropical and arid? High Na and Cl in coastal precip? Changes from precipitation ….. surface water…….. ground water Carbonate vs. granitic water NOT DISSOLVED BUT STILL IN WATER • Immiscible liquids…. NAPL (organics) • Non Aqueous Phase Liquids (denser than water, DNAPL; lighter than water LNAPL • Common contaminants • Suspended sediments (particulates) … to water CHEMICAL SPECIATION • Determine the forms of all the entities in water. What could they be: o Monoatomic ions (Na+, Ca+2) o Polyatomic ions … HCO3- , SO4, OH▪ Special subgroup – the oxyanion…. o Complexes o Neutral species, H4SiO4o o Sorbed species………. Attached to mineral surfaces • Example – what species may exist in H2O? o H+, OH-, H2O • in a mixture of Ca-CO2-H2O? (all the possible combinations) • Ca, C, O, CaCO3, CaOH, H, OH…. • Depends on pH CHEMICAL SPECIATION WHAT SPECIES would we find in water????? –Railsback and the ionic potential (z/r) Ionic potential (z/r) = (ionic charge/ionic radius) – ratio of electric charge to radius of ion This is a guideline! (start with END MEMBERS) • Low (z/r) – (K, Na, Sr) − Not very much charge for a big cation – weak bonds with oxygen (charge can’t reach out very far ) − Bond only weakly to O if at all − Why…. CHEMICAL SPECIATION • High (z/r > 15) (P, N ,S) − charge is “focused” – small size for the charge.. − forms strong bond with oxygen – but repulses other cations − So stable as PO43-, SO42-, NO3− But positive charge incompletely shielded – repulse each other • intermediate (z/r) (Al, Ti) – (Fe, Mn) − relatively strong cation-oxygen bonds (rutile, TiO2) − form lattice structures well – shielding creates stable structure − common as oxides, hydroxides CHEMICAL SPECIATION Types of reactions that occur • Mineral dissolution 
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