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Water STRUCTURE
WHY DO WE NEED TO DO
THIS AGAIN!!!
Properties of water
Very polar

Oxygen is highly electronegative
H-bond donor and acceptor
High b.p., m.p., heat of vaporization, surface tension
Water dissolves polar compounds

solvation shell
or
hydration shell
Non-polar substances are insoluble in water
Many lipids are amphipathic
How detergents work?
Hydrogen Bonding of Water
One H2O molecule can associate with 4 other H20 molecules

Ice: 4 H-bonds per water molecule
Water: 2.3 H-bonds per water molecule
Crystal lattice of
Biological
Hydrogen Bonds
non-covalent interactions
Relative Bond Strengths
Bond type

kJ/mole

H3C-CH3

88

H-H

104

Ionic

40 to 200

H-bond

2 - 20

Hydrophobic interaction

3 -10

van der Waals

0.4 - 4
Ionization of Water
Ionization of Water
H20 + H20
H2 0
Keq= [H+] [OH-]
[H2O]

H3O+ + OHH+ + OHKeq=1.8 X 10-16M
[H2O] = 55.5 M

[H2O] Keq = [H+] [OH-]
(1.8 X 10-16M)(55.5 M ) = [H+] [OH-]
1.0 X 10-14 M2 = [H+] [OH-] = Kw
If [H+]=[OH-] then [H+] = 1.0 X 10-7
pH Scale
 Devised by Sorenson (1902)
 [H+] can range from 1M and
1 X 10-14M
 using a log scale simplifies notation
 pH = -log [H+]
Neutral pH = 7.0
Weak Acids and Bases
Equilibria
•Strong acids / bases – disassociate completely
•Weak acids / bases – disassociate only partially
•Enzyme activity sensitive to pH
• weak acid/bases play important role in
protein structure/function
Acid/conjugate base pairs
HA + H2O
HA

A- + H3O+
A- + H+

HA = acid ( donates H+)(Bronstad Acid)
A- = Conjugate base (accepts H+)(Bronstad Base)

Ka = [H ][A ]
[HA]
+

-

pKa = - log Ka

Ka & pKa value describe tendency to loose
H+
large Ka = stronger acid
small Ka = weaker acid
pKa values determined by
titration
Phosphate has three ionizable H+ and
three pKas
Buffers
Buffers are aqueous systems that resist

changes in pH when small amounts of a
strong acid or base are added.
A buffered system consist of a weak acid and

its conjugate base.
The most effective buffering occurs at the

region of minimum slope on a titration
curve
(i.e. around the pKa).
Buffers are effective at pHs that are

within +/-1 pH unit of the pKa
Henderson-Hasselbach Equation
1) Ka = [H ][A ]
[HA]
+

-

HA = weak acid
A- = Conjugate base

2) [H+] = Ka [HA]
[A-]
3) -log[H+] = -log Ka -log [HA]
[A-]
4) -log[H+] = -log Ka +log [A-]
[HA]
5) pH = pKa +log [A-]
[HA]

* H-H equation describes
the relationship between
pH, pKa and buffer
concentration
Case where 10% acetate ion 90% acetic
acid

• pH = pKa + log10

[0.1 ]
¯¯¯¯¯¯¯¯¯¯

[0.9]

• pH = 4.76 + (-0.95)
• pH = 3.81
Case where 50% acetate ion 50% acetic
acid

• pH = pKa + log10

[0.5 ]
¯¯¯¯¯¯¯¯¯¯

[0.5]

• pH = 4.76 + 0
• pH = 4.76 = pKa
Case where 90% acetate ion 10% acetic
acid

• pH = pKa + log10

[0.9 ]
¯¯¯¯¯¯¯¯¯¯

[0.1]

• pH = 4.76 + 0.95
• pH = 5.71
Cases when buffering fails

• pH = pKa + log10

[0.99 ]
¯¯¯¯¯¯¯¯¯¯

[0.01]

• pH = 4.76 + 2.00
• pH = 6.76
• pH = pKa + log10

[0.01 ]
¯¯¯¯¯¯¯¯¯

[0.99]

• pH = 4.76 - 2.00
• pH = 2.76
Water Structure and Properties

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Water Structure and Properties

  • 1.
  • 3. WHY DO WE NEED TO DO THIS AGAIN!!!
  • 4. Properties of water Very polar Oxygen is highly electronegative H-bond donor and acceptor High b.p., m.p., heat of vaporization, surface tension
  • 5.
  • 6. Water dissolves polar compounds solvation shell or hydration shell
  • 7. Non-polar substances are insoluble in water Many lipids are amphipathic
  • 9. Hydrogen Bonding of Water One H2O molecule can associate with 4 other H20 molecules Ice: 4 H-bonds per water molecule Water: 2.3 H-bonds per water molecule
  • 10.
  • 13.
  • 15. Relative Bond Strengths Bond type kJ/mole H3C-CH3 88 H-H 104 Ionic 40 to 200 H-bond 2 - 20 Hydrophobic interaction 3 -10 van der Waals 0.4 - 4
  • 17. Ionization of Water H20 + H20 H2 0 Keq= [H+] [OH-] [H2O] H3O+ + OHH+ + OHKeq=1.8 X 10-16M [H2O] = 55.5 M [H2O] Keq = [H+] [OH-] (1.8 X 10-16M)(55.5 M ) = [H+] [OH-] 1.0 X 10-14 M2 = [H+] [OH-] = Kw If [H+]=[OH-] then [H+] = 1.0 X 10-7
  • 18. pH Scale  Devised by Sorenson (1902)  [H+] can range from 1M and 1 X 10-14M  using a log scale simplifies notation  pH = -log [H+] Neutral pH = 7.0
  • 19. Weak Acids and Bases Equilibria •Strong acids / bases – disassociate completely •Weak acids / bases – disassociate only partially •Enzyme activity sensitive to pH • weak acid/bases play important role in protein structure/function
  • 20.
  • 21. Acid/conjugate base pairs HA + H2O HA A- + H3O+ A- + H+ HA = acid ( donates H+)(Bronstad Acid) A- = Conjugate base (accepts H+)(Bronstad Base) Ka = [H ][A ] [HA] + - pKa = - log Ka Ka & pKa value describe tendency to loose H+ large Ka = stronger acid small Ka = weaker acid
  • 22. pKa values determined by titration
  • 23. Phosphate has three ionizable H+ and three pKas
  • 24. Buffers Buffers are aqueous systems that resist changes in pH when small amounts of a strong acid or base are added. A buffered system consist of a weak acid and its conjugate base.
  • 25. The most effective buffering occurs at the region of minimum slope on a titration curve (i.e. around the pKa). Buffers are effective at pHs that are within +/-1 pH unit of the pKa
  • 26. Henderson-Hasselbach Equation 1) Ka = [H ][A ] [HA] + - HA = weak acid A- = Conjugate base 2) [H+] = Ka [HA] [A-] 3) -log[H+] = -log Ka -log [HA] [A-] 4) -log[H+] = -log Ka +log [A-] [HA] 5) pH = pKa +log [A-] [HA] * H-H equation describes the relationship between pH, pKa and buffer concentration
  • 27. Case where 10% acetate ion 90% acetic acid • pH = pKa + log10 [0.1 ] ¯¯¯¯¯¯¯¯¯¯ [0.9] • pH = 4.76 + (-0.95) • pH = 3.81
  • 28. Case where 50% acetate ion 50% acetic acid • pH = pKa + log10 [0.5 ] ¯¯¯¯¯¯¯¯¯¯ [0.5] • pH = 4.76 + 0 • pH = 4.76 = pKa
  • 29. Case where 90% acetate ion 10% acetic acid • pH = pKa + log10 [0.9 ] ¯¯¯¯¯¯¯¯¯¯ [0.1] • pH = 4.76 + 0.95 • pH = 5.71
  • 30. Cases when buffering fails • pH = pKa + log10 [0.99 ] ¯¯¯¯¯¯¯¯¯¯ [0.01] • pH = 4.76 + 2.00 • pH = 6.76 • pH = pKa + log10 [0.01 ] ¯¯¯¯¯¯¯¯¯ [0.99] • pH = 4.76 - 2.00 • pH = 2.76