hints - Useful quantities: Kinetics Useful quantities: k(T)...

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Unformatted text preview: Useful quantities: Kinetics Useful quantities: k(T) = Z.p f(T); Periodic Table with electronegativities Periodic Table with electronegativities † k For A(B, Rate = -d[A]/dt = d[B]/dt = k[A] A + B ( C + D with rate constants k 2 , k -2 . d[C]/dt = - d[A]/dt = k 2 [A][B]- k-2 [C][D] Integrated: [A] = [A0] exp[-kt] IP(eV)+EA(eV))/2 (Mulliken) E.N. ! (IP(eV)+EA(eV))/2 (Mulliken) .00175 * {ns*IPs + np* IPp}/ (np+ns) . ! 0.00175 * {ns*IPs + np* IPp}/ (np+ns) E.N Z = (&d2)*vrms*concentration f(T) = exp[-Ea /RT] , When d[A]/dt = 0 k 2 /k-2 = K = exp[-"G / RT] A ( B with forward/backward rate constants k1 , k-1 . d[B]/dt = - d[A]/dt = k1 [A]- k-1[B] When d[A]/dt = 0 k1 /k-1 = K = exp[-"G / RT] Integrated: -1 [A] = k2 t + [A 0] -1 if k-2 ! 0 Thermodynamic Formulas Mass-action law: 2 1 mole ! 6.02.10P 3 obmass jects I .10-3kJ/Joule.seamu ( 4 mole) c h ! 6.62 H 1310 1.01 e ! 1.60.10-19 51oulombs C9 Li 6.94 .1900 7 kg 01 1 amu ! 1.66 0-2 Be 9. 799 10 g melectrBn ! 9.10.10-31k.8 o C 1088 12.0 N 14 08 /s c = 2.99792458.102 m14.0 O 1314 16.0 Ry ! 2.F.10-1816oules 19.0 2 J 82 20 0- C m 1 DebyNe 3.30.179 30 23..2 e! 57 27 e 1 eV/atAl ! 96.57kJ/mol.0 om 41 m -d.1 R = 0.0K2 l-atm/(8 ole39eg) 8 Cl31 J/(mole-deg).5 1254 35 or 8 . 58 l 48 F = 96Ca5 C/mo9e 40.1 radius Å 0.25 1.45 1.05 0.85 0.70 0.65 0.60 0.57 0.51 1.25 2.27 1.00 1.80 1.40 1.40 Fe Cr 761 652 55.9 52.0 Some heat1 of rea! t6on "H23 objectsle Some heats of reaction "H in kJ/mole s mole c i .02.10 in kJ/mo radius Mg + CO2 (h MgO2 .10-34 Joule.sec -230Mg + CO2 ( MgO2 + C -230 Å ! 6.62 + C 0.MgO ( 2 MgO + O . -19 2 25 2 40 e ! 1.60 10 Coulombs 402 MgO2 ( 2 MgO + O2 2 1.45 1 1.05O2 ( CO2 amu ! 1.66.10-27 kg )394C + O2 ( CO2 C+ )394 0.2H4 (liq) + Hm (g) ( 2 NH3.10.10-31kg -143 2H4 (liq) + H2 (g) ( 2 NH3 (g) N 85 N -143 2 electron ! 9 (g) 0.70 2NH 2N 0.65 3 (g) + 3/2 O2 2.99792458).103Hm/s g) -634 H3 (g) + 3/2 O2 (g) ( N2 (g) + 3H2O (g) -634 c = (g) ( N2 (g + 8 2O ( 0.60 2 57 H ( ) + .10-18 +484 H2O (g) ( 2 H2 (g) + O2 (g) 2 +484 0.H2O (g) ( 2Ry2 !g2.2O2 (g) Joules 0.51 1 Debye es 3.30.10-30 C.m Gas ! Gases 1.25 = nRT 1 eV/atom ! (96.5)kJ/mole2 PV P = nRT / V-nb - a (n/V) PV = nRT P = nRT / (V-nb) - a (n/V)2 2.27 3 R m vrms2 p l- atom moletomic E = / kT = 1/2 = 0.082 eratm/((mona-deg)gas)E = 3/2 kT = 1/2 m vrms2 per atom (monatomic gas) 1.00 2 orP8.31 Jv ole-deg) /(m Cv = -V Cv = Cp - nR = Cp - PV vrms="(3kBT/m) 1.80 = Cp - nR FCp 96485 C/ms="(3kBT/m) rm = ole 1.40 -23 1.40 Volume ratio kB= spherex f = 1.J/K of a 1.38 : 10 35 Volume ratio of a sphere: f = 1.35 (excluded volume / sphere volume) (excluded volume / sphere volume) Quantum Mechanics and Spectroscopy Quantum Mechanics and Spectroscopy "x"p # h n2/(8mL2) 1/2) !$ ="x"p En = -Ry/p 2 mv !Lasp r==hc$ /2L = c c #h n= En = -Ry/n2 !Laser = cn/2L e / n !$ 12n2/(v2 + 2)(x) E = KineticV(r)otential = 1/ mv2 + V(x) 2/ r E = Kineti! + Potential = h /2 m 8mLV E = hc H atom: + P = -e H atom: V(r) = -e2/r En = 2 % = 2&! = "(kn µ) !%(n+=m1m2!(m11/2) ) % =ratomic= "('0µ)2 /(& m=m1Ze2f) m1+m2) E/ = µ1/2)=h / (n++m2 2&! ! n k/ h µe e2 m f/( ratomic! n '0 h2 /(& me e2 Zeff) avelengths: Dipole r p = mv = qp = h/$ Colors and wavelengths: p = -it!##1#x E2 = m2c4 + p2c2 "!" / "!"t # 1 " ~t# n "E"t # h * ~ sin(n&x/L) for particle in ent ox ab *E"sin(h &x/L) for particle in a box transparent 350 nm UV transpar green-yellow nm 400 violet green-yellow p = */$= E h p = h/$ En* yellow-orange nm H*n =blue n P(x) = |*(x)|2 $ 0 450 yellow-orange (free Harticle) n*n P(x) = |*(x)|2 $ 0 pn (free particle) een orange-red 490 nm blue-green orange-red red 550 nm green red ellow violet 570 nm green-yellow violet dark blue 580 nm yellow dark blue bl ue 600 nm orange blue green 650 nm red green transparent 700 nm IR transparent olor Transmitted coWavel. p Absorbed Color =Tm2c4 +tted 2 l. = -i! #/#x E2 ransmi p2c col. H = E + PV G = H -TS K= [C]nC [D]nD = k /k 1 -1 [A]nA [B]nB n n n dWmech = - Pext dV "E = q + w dE = dQ + dW Energy = (active number of degrees of freedom)* (kB/2) * T T = (#E/#S)v Q = heat absorbed by system, W = work done on system; "E = Cv"T; Keq = exp[ "Grx = "G0 n or Q = P C P D / PA A PB B for nAA+nBB(nCC+nDD C D "G(0) rx / RT ] "H = Cp"T; Probability2/Probability1 = exp[-(E2-E1)/RT] = exp[-"E/RT] (Boltzmann law) rx + RTln(Q) E=3nRT/2 (ideal monatomic gas) lnP = -"Gvap/RT = -"Hvap/RT + "Svap/R Q = C "T (C = heat capacity) q = Q/n (intensive quantity) Table of thermodynamic quantities at 298 K, 1 atm. odynamic quantities at 298 K, 1 atm. Table of therm Colligative properties and phase transitions "Hf "Gf kJ/mole kJ/mole H2O (liq) -286 -237 I2 (g) 62.5 19.4 IBr (g) 40.9 3.8 Br2 (g) 30.8 3.1 O2 (g) 0 0 N2O (g) 82.0 104.2 NO2 (g) 33.1 51.31 N2O4 (g) 9.16 97.89 N2H4 (l) not given here H2O (g) see table of heats of rx. NH3 (g) -46 -16.5 CO2 (g) -394 -394 C2H4 (g) 52 68 C4H4 (g) 428 C2H2 (g) 226.7 209.2 Al2O3 (s) -1676 -1582 Al (s) 0 0 Fe2O3 (s) -826 -740 Fe (s) 0 0 Compund Sf J/mole-K 70 261.5 259.0 246.3 205 220 240 304.29 121 188 192.5 214 219 200.9 51 28 90 27 Compup C nd "Hf "Gf Sf Cp J/mole-KkJ/mole P kJ/molePo J/mole-K P) = -"Hvap /RT + "S vap /R ln( J/mole-K + A = 37 A A H2O75 (liq) -286 -2 75 o+ +70 o =+ BPB 5 I2 [(or 4.2 J/g-K.5 Ptot 19.4 A PA g) 62 ] 261. [or 4.2 J .*R ] Kb=M.W/g-KTb2 /"Hvap = IBr (g) 40.9 "Tb 3.8 iKb mA 259.0 nA Br2 (g) 36 30.8 "Tf 3= -iKf mA 246.3Mole fr6 ion: +(,) = .1 3act nA + nB O2 (g)9.3 2 0 0 29.3 Posmotic = MRT 205 N2O 38.5 (g) 82.0 104.2 220 38P .5 = n gas gas KH NO2 37.2 (g) 33.1 51.31 240 37.2 N2O47.3 7 (g) 9.16 97.89 304.29 77.3 Group names: N2H4 (l) not given here 139 121 139 Solubility x. 188 H2O (g) 33.6 see table of heats of rproducts: 33.6 C2v (e.g. water) Co(OH)3 2.5. NH3 (g) 35 -46 -16.5 192.510-43 35 CO37(g) -394 -394 214 . -6 37 D%h (homonuclear 2 Ca(OH)2 1.3 C2H43(g) 52 68 219 10 43 4 diatomic) C4H4 (g) 428 Cd(OH)2 5.9.10-15 Oh (octahedron) C2H44(g) 226.7 209.2 200.9. -31 44 2 Cr(OH)3 6.7 10 Al2O15s) -1676 13 ( -1582 51 115 .10-5 PbCl0 1.6 Al (s) 4 2 0 28 24 Td (tetrahedron) 2 (assuming molarities) Fe2O3 2s) -826 15 ( -740 90 152 Fe (s) 3 2 0 0 27 23 ...
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This note was uploaded on 10/10/2011 for the course CHEMISTRY 202 taught by Professor Grubele during the Spring '11 term at University of Illinois, Urbana Champaign.

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