ha a - + h +
DESCRIPTION
Determination of dissociation constants of uniprotic acids with known spectrum of acidic or basic component. HA A - + H +. C t [H + ]. C t K a. [ HA] =. [ A - ] =. [ H + ] + K a. [ H + ] + K a. s HA. s A. c A. c HA. =. +. - PowerPoint PPT PresentationTRANSCRIPT
![Page 1: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/1.jpg)
Determination of dissociation constants of uniprotic acids with known spectrum of
acidic or basic component
![Page 2: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/2.jpg)
Determination of dissociation constants of uniprotic acids with known spectrum of acidic or basic component
HA A- + H+
[HA] =
Ct [H+][H+] + Ka
[A-] =
Ct Ka
[H+] + Ka
D XHA XA= +
cHA
sHA
= cA
sA
+
R = D - XHA = D - cHAsHAT
![Page 3: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/3.jpg)
Determination of dissociation constants of uniprotic acids with known spectrum of acidic or basic component
R = D - XHA = D - cHAsHAT
cHA =f (Ka)
sHAD
![Page 4: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/4.jpg)
rafa_Ka.m
Determination of Pka value for an uniprotic acid with known spectrum of HA
species
![Page 5: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/5.jpg)
Calling function rafa_Ka
![Page 6: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/6.jpg)
![Page 7: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/7.jpg)
![Page 8: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/8.jpg)
![Page 9: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/9.jpg)
?Investigate the effects of extent of spectral overlapping on the determined pKa value by RAFA
![Page 10: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/10.jpg)
Di-protic Acids
[H]2 + Ka1 [H] + Ka1 Ka2
Ct [H]2
[H2A] =
[H]2 + Ka1 [H] + Ka1 Ka2
Ct Ka1 [H]2
[HA] =
[H]2 + Ka1 [H] + Ka1 Ka2
Ct Ka1 Ka2[A] =
R = D - XH2A = D - cH2AsH2AT
cH2A =f (Ka1, Ka2)
![Page 11: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/11.jpg)
pKa1= 3.0 pKa2=4.0
![Page 12: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/12.jpg)
pKa1= 3.0 pKa2=4.5
![Page 13: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/13.jpg)
pKa1= 3.0 pKa2=5.0
![Page 14: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/14.jpg)
pKa1= 3.0 pKa2=5.5
![Page 15: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/15.jpg)
pKa1= 3.0 pKa2=6.0
![Page 16: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/16.jpg)
pKa1= 3.0 pKa2=6.5
![Page 17: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/17.jpg)
pKa1= 3.0 pKa2=7.0
![Page 18: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/18.jpg)
Determination of amount and pKa values of an acid in a mixture with known spectrum of
its components
![Page 19: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/19.jpg)
HA A- + H+
[HA] =
Ct [H+][H+] + Ka
[A-] =
Ct Ka
[H+] + Ka
XHA XAD = +
cHA
sHAcA
sA
= +
R = D - XHA - XA = D - cHAsHAT- cA sA
T
Determination of amount and pKa values of an acid in a mixture with known spectrum of its components
Interferences+
+ Interferences
![Page 20: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/20.jpg)
pH-metric titration of a mixture containing an acid with known spectrum of components
D sHA sA
R = D - XHA -XA= D - cHAsHAT - cA sA
T
cHA =f (C0,Ka) cA =f (C0,Ka)
![Page 21: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/21.jpg)
rafa_CKa.m
Determination of concentration and Pka
values for an uniprotic acid with known spectrum of
HA and A component
![Page 22: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/22.jpg)
Calling function rafa_CKa
![Page 23: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/23.jpg)
![Page 24: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/24.jpg)
![Page 25: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/25.jpg)
![Page 26: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/26.jpg)
![Page 27: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/27.jpg)
![Page 28: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/28.jpg)
?Use RAFA_CKa and determine the amount and pKa values of a known acid in an unknown mixture
![Page 29: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/29.jpg)
Rank Annihilation Factor Analysis for Spectrophotometric Study of Complex Formation Equilibria
Anal. Chim. Acta486, 109-123, 2003
![Page 30: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/30.jpg)
M + nL MLnM + nL MLn
[M] [L][MLn]
Kf= n[M] [L][MLn]
Kf= n
CL = [L] + [ [MLn]
CM = [M] + [ [MLn]
Kf[L]n+1 + (nKfCM – KfCL) [L]n + [L] –CL = 0
[MLn] = Kf CM[L]n / (1+Kf[L]n)
[M] = CM / (1 + Kf[L]n)
One-step complex formation equilibria
![Page 31: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/31.jpg)
XMLnD = XL +
cL
sLcMLn
sMLn
= +
R = D - XL = D - cLsLT
+ Interferences
cL= f(Kf,n)
Rank Annihilation Factor Analysis for Spectrophotometric Study of Complex Formation Equilibria
![Page 32: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/32.jpg)
One step complex formation (n=2)
M + 2L MLM + ML2
[L] [M]
[ML2]
CL=0.001KL=106.
5
![Page 33: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/33.jpg)
rafa_MLn.m
Determination of stoichiometry and
formation constant values for an MLn complex with known spectrum of ligand
![Page 34: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/34.jpg)
![Page 35: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/35.jpg)
![Page 36: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/36.jpg)
![Page 37: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/37.jpg)
![Page 38: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/38.jpg)
![Page 39: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/39.jpg)
n=1
n=2
n=3
n=4n=
5
![Page 40: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/40.jpg)
![Page 41: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/41.jpg)
?Create the data for ML3 system and use RAFA for determination of Kf and its stoichiometry.
![Page 42: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/42.jpg)
MLn.m
Simulation of MLn complex formation system
![Page 43: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/43.jpg)
Calling function MLn
![Page 44: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/44.jpg)
![Page 45: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/45.jpg)
![Page 46: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/46.jpg)
![Page 47: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/47.jpg)
![Page 48: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/48.jpg)
![Page 49: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/49.jpg)
![Page 50: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/50.jpg)
![Page 51: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/51.jpg)
![Page 52: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/52.jpg)
[M] [L][ML]
K1=
[ML] [L][ML2]K2=
CL = [L] + [ML] + 2 [ML2]CM = [M] + [ML] + [ML2]
K1K2[L]3 + (K1(1+K2(2CM –CL)))[L]2 + (1+K1(CM –CL))[L]–CL = 0
ML + L ML2
M + L ML
Two successive step complex formation
![Page 53: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/53.jpg)
A = AL + AML + AML2 + R
= L [L]T + ML [ML]T + ML2 [ML2]T + R
= E CT + R
Two successive step complex formation
R = D - XL = D - cLsLT
cL= f(K1 , K2)
![Page 54: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/54.jpg)
Determination of dissociation constants of uni-protic acids without known spectrum
![Page 55: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/55.jpg)
12
543
54
123
11
111
52
0.20.51
0.1 0.2 0.3 0.40.1 0.3 0.4 0.2
0.1 0.2 0.3 0.40.1 0.3 0.4 0.2
0.60.30.20.150.12
1.70.80.50.350.26
2.31.10.70.50.38
1.40.80.60.50.44
=
0.60.60.60.60.6
1.71.61.51.41.3
2.32.22.12.01.9
1.41.61.82.02.2
=
12
543./
12
543./
A simple mathematical rule
![Page 56: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/56.jpg)
12
543
54
123
12
543./
11
111
52
0.20.51
00
000
3.260.26
-1.54-1.24-0.74
12
543
54
123
32
451./
0.331
1.250.83
1.662
0.250.43
-0.746 0.1980.538
-1.212-1.0621.538
-0.076 1.924-0.276 0.174
Mean centering
Mean centering
Rank = 2 Rank = 2 Rank = 1
Rank = 2 Rank = 2 Rank = 2
![Page 57: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/57.jpg)
HA A- + H+
[HA] =
Ct [H+][H+] + Ka
[A-] =
Ct Ka
[H+] + Ka
D XHA XA= +
cHA
sHAcA
sA
= +
D’ = D ./ cHA
Determination of dissociation constants of uni-protic acids
Mean centering (D’)
cHA = f(Ka)
![Page 58: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/58.jpg)
Titration of an uni-protic acid or a mixture containing an uni-protic acid
![Page 59: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/59.jpg)
Rafa_mcKa.m
Determination of dissociation constants of
uni-protic acids
![Page 60: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/60.jpg)
Calling function rafa_mcKa
![Page 61: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/61.jpg)
![Page 62: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/62.jpg)
![Page 63: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/63.jpg)
![Page 64: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/64.jpg)
![Page 65: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/65.jpg)
![Page 66: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/66.jpg)
?Use mean centering based method for determination of acidity constant of an uniprotic acid in a mixture
![Page 67: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/67.jpg)
Determination of dissociation constants of di-protic acids without known spectrum
![Page 68: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/68.jpg)
cHA =f (Ka1, Ka2)
Determination of dissociation constants of di-protic acids without known spectrum
D’ = D ./ cHA Mean centering (D’)
![Page 69: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/69.jpg)
Rafa_mcH2A.m
Determination of dissociation constants of
di-protic acids
![Page 70: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/70.jpg)
Calling function rafa_mcH2A
![Page 71: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/71.jpg)
![Page 72: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/72.jpg)
![Page 73: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/73.jpg)
![Page 74: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/74.jpg)
![Page 75: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/75.jpg)
![Page 76: HA A - + H +](https://reader036.vdocuments.site/reader036/viewer/2022081511/56814851550346895db56363/html5/thumbnails/76.jpg)
?Use mean centering based method for determination of acidity constant of an di-protic acid in a mixture