7/19/2011. Models of Solution Chemistry- III Acids and Bases

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1 Models of Solution Chemistry- III Acids nd Bses Ionic Atmosphere Model : Revisiting Ionic Strength Ionic strength - mesure of totl concentrtion of ions in the solution Chpter i μ ( ) 2 c i z c concentrtion of the ith species i zi chrge on the ith species Ionic strength Increses s the number of ions incresed Incresing ionic strength reduces ttrction between positive nd negtive ions Strongly influences the equilibrium of ny chemicl rection in queous solution Ionic Atmosphere Model : Revisiting Ionic Strength μ 1 2 i ( ) 2 c i z Chpter 8 Ionic strength clcultion - one hlf the sum of the concentrtion of ech ion multiplied by the chrge of the ion squred c i concentrt ion of the ith species; z chrge on the ith species i Wht is the ionic strength of 0.10 M NNO 3 nd 0.20 M N 2 SO 4? 0.50 M KCl nd 0.80 M CBr 2? 1

2 Clcultion Ionic Strength Electrolytes 1 formul unit of NCl dissocites to produce exctly 1 N + ion nd 1 Cl ion 1:1 electrolyte CBr 2-1:2 electrolyte N 2 SO 4-2:1 electrolyte N 3 PO 4-3:1 electrolyte Electrolyte Molrity Ionic Strength 1:1 M M 1:2 M 3M 1:3 M 6M 2:2 M 4M Chpter 8 Activity Coefficients To ccount for the effect of ionic strength the concentrtions re replced with ctivities A X [X] γ X γ X Activity coefficient of X - mesure of the devition from the idel behvior - t low ionic strength γ X pproches to unity A+ bc cc + dd We will express the chemicl equilibrium Chpter 8 [ A ] [ A ] K [ A [ A c C A ] d D b B] d [C] γ [D] γ D b [A] [B] γ c C γ A B Activity Coefficients For exmple, Chpter 8 CSO 4 (s) K SP C 2+ (q) + SO 4 2- (q) 2+ [ A 2+ ][ A 2- ] [C ]( γ 2+ )[SO ]( γ 2 C SO4 C 2 4 SO4 The ctivity it coefficients re obtined from the ionic tmosphere model using extended Debye-Hückel eqution tht reltes chrge (z), size of the ionic tmosphere (α), nd the ionic strength (μ) z μ log γ t 25 C μ 1 + α 305 Units : z no unit needed α in pm μ in M ) 2

3 Acids nd Bses Arrhenius Definitions Definition 1: Arrhenius definitions of cids nd bses Acids produce H + ions (or hydronium ions H 3 O + ) HA (s) + H 2 O (l) H 3 O + (q) + A - (q) Bses produce OH ions BOH B + + OH Exceptions: Some bses don t hve hydroxide ions! e.g. Ammoni NH 3 Arrhenius Definitions Arrhenius cid is substnce tht produces H + (H 3 O + ) in wter Arrhenius bse is substnce tht produces OH in wter 3

4 Brønsted Lowry Definitions Definition 2: Brønsted Lowry Acids proton donor Bses proton cceptor bse cid conjugte cid conjugte bse Brønsted Lowry Definitions Conjugte pirs Acids proton donor Bses proton cceptor HCO )+HO(l) )+CO 3 (q) 2 H 3 O + (q) 2 3 (q) cid bse conjugte cid conjugte bse Find Out Conjugte Acid-Bse Pirs 1. HCl(q), Cl (q) nd H 2 O(l), H 3 O + (q) 2. H 2 O(l), OH (q) nd NH 3 (q), NH 4+ (q) 3. HCl(q), Cl (q) nd NH 3 (q), NH 4+ (q) 4. H 3 PO 4 (q), H 2 PO 4 (q) nd H 2 O(l), H 3 O + (q) 5. H 2 PO 4 (q), HPO 2 4 (q) nd H 2 O(l), H 3 O + (q) 4

5 Find Out Conjugte Acid-Bse Pirs Lewis Acid nd Lewis Bse Definitions Definition 3: Lewis cid nd Lewis bse Lewis cid : A chemicl species tht ccepts n electron pir Lewis bse : A chemicl species tht dontes n electron pir Lewis Acid nd Lewis Bse Definitions 5

6 Lewis Acid nd Lewis Bse Definitions Fe N C Dioxygen Fe center The heme group in hemoglobin cn interct with O 2 nd dco CO. The Fe ion in hemoglobin is Lewis cid O 2 nd CO cn ct s Lewis bses ph Scle The ph scle is to express the strength of cids nd bses with esily hndled numbers. Insted of using very smll numbers, we just use the negtive power of 10 of the Molrity of the H + (or OH ) ion. Under 7 cid 7 neutrl Over 7 bse Strength: The tendency to donte or ccept proton. Wek cid hs wek proton-donting tendency; while strong cid hs strong proton-donting tendency. The definition is true for bses: strong bse hs strong proton ccepting tendency. One cn only define strength in reltive sense. Strength mesured reltive to some reference, in the present cse, the solvent wter. Strength is judged on both the cid nd bse involved in n cid-bse rection. 6

7 Exmple of strong cid such s HCl. Cl H + H + H + Cl Cl H + Cl H+ Cl Exmple of n wek cid such s cetic cid. CH 3 COO CH 3 COO H + H + CH 3 COO H + CH 3 COO H + CH 3 COO H + Quntittive Determintion of Strength by Dissocition Constnt Consider the first step of the dissocition of ny cid HA (q) K + - [H ][A ] K [HA] H + (q) + A - (q) The lrger K, the stronger the cid; the smller K, the weker the cid. 7

8 Acids Strength: The tendency to donte or ccept proton. pk - log K Thus, the lrger pk, the weker the cid; the smller pk, the stronger the cid. Similrly, ph - log [H + ] poh - log [OH ] px - log X Bses Strength: The tendency to ccept proton. K b A (q)+ H 2 O (l) HA (q) + OH (q) [HA][OH ] Kb [A ] pk b - log K b The lrger pk b, the weker the bse; the smller pk b, the stronger the bse. Self ioniztion of wter Neutrlity is defined by the condition: [H + ] [OH - ]. Wter is mphoteric K w H 2 O (l) H + (q) + OH + (q) K [H ][OH ] w 8

9 Self ioniztion of wter Show tht t neutrl condition, ph7.00 K w + 14 K w [H ][OH ] 10 H 2 O (l) H + (q) + OH (q) Neutrlity is defined by the condition: [H + ] [OH - ] i.e. [H + ] or, [H + ] 10 7 or, ph -log[h + ] 7 Conjugte Acids nd Bses H + + A HA 1/K H 2 O H + + OH K w A- + H 2 O HA + OH K b K K b K w The stronger n cid, the weker is the conjugte bse, nd vice vers Free Energy Chnge in n Acid Dissocition HA (q) K H + (q) + A - (q) pk - log K Gibb's free energy chnge due to the dissocition, o ΔG RT ln K 2.303RT log K where R nd T re universl gs constnt -1-1 ( J K mol nd temperture, respectively. 9

10 Free Energy Chnge in n Acid Dissocition K HA (q) H + (q) + A - (q) Clculte the free energy chnge ssocited to the dissocitions of the following cids with the given pk s cetic (ethnoic) cid CH 3 COOH 4.75 citric cid C 6 H 8 O crbonic cid H 2 CO hydrochloric cid * HCl -4 hydrogen sulfide H 2 S 7.04 ph Clcultions Strong cid nd strong bse Sitution 1: Equivlence point Eqution: H 2 O H + + OH - x x x 2 K w x10 ph7.00 ph Clcultions Wek cid nd strong bse Sitution 2: Before dding bse Eqution: HA H + + A - F x x x 2 x K x? F x ph H? Let K nd we strted from M HA 10

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