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BT-202 Biochemistry Aug 16, 2011

Bt 202 aug 12 2011 ppt1997-2004

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Page 1: Bt 202 aug 12 2011 ppt1997-2004

BT-202 Biochemistry

Aug 16, 2011

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• Acids and Bases: Definitions• Ionization of water• pH Scale• Dissociation of Weak acids

and bases• Buffers

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Vinegar and Aspirin

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Soaps, toothpaste and cleaning agents.

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HF + H2O H3O+ + F-

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Learning check!

Label the acid, base, conjugate acid, Label the acid, base, conjugate acid, and conjugate base in each reaction:and conjugate base in each reaction:

• H2SO4 + H2O HSO4- + H3O+

• HCl + OH- Cl- + H2O

• HCl + NH3 Cl- + NH4+

• NH3 + H2O NH4+ + OH-

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• Identify the conjugate base in each of the pairs below?

• RCOOH, RCOO-

• RNH2, RNH3+

• H2PO-,H3PO4

• H2CO3, HCO3-

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Proton donor

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Proton Hopping•Ionization can be measured by its electrical conductivity.•Movement of hydronium ion is very fast due to “proton hopping”. •No single proton moves over a long distance but a series of proton hops between water molecules which are hydrogen bonded.

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• Most of the acid base reactions in the aqueous solution are exceptionally very fast.

• Proton hopping also plays a role in biological proton transfer reactions.

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• Reversible ionization is very crucial to the role of water in cellular function.

• We need to express the extent of ionization in quantitative terms.

• The position of equilirium for any chemical reaction is given by its EQUILIBRIUM CONSTANT, Keq.

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• For any generalized reaction:

Equilibrium constants are dimensionless but biochemists have retained the concentration units (M) or molarity.

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• Equilibrium constant for a reversible reaction of water is:

Keq = [H+] [OH-]

[H2O]

In pure water at 25°C, the concentration of water is 55.5 M.

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• At this pH the concentration of [H+] and [OH-] is 1 X 10-7.

• Whenever [H+] is greater than 1 X 10-7 [OH-] is less and visa versa.

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Learning check!

• What is the concentration of H+ in a solution of 0.1 M NaOH?

• What is the [H+] of human saliva if its [OH-] is 4 x 10-8 M? Is human saliva acidic, basic, or neutral?

• What is the [H+] of a sample of lake water with [OH-] of 4.0 x 10-9 M? Is the lake acidic, basic, or neutral?

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Learning check!

• What is the concentration of OH- in a solution with an H+ concentration of 1.3 X 10-4M?

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If an acidic solution is defined as a solution water where H3O+ is greater than OH-, what can be said of an acidic solution?

[OH-]>[H3O+]

The concentration of H3O+ must be greater than 10-7.

The concentration of H3O+ is always 10-7 if the solution is made in water.

The solution feels slippery and might taste bitter.

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pH of some aqueous fluids.pH scale ranges from 0-14.

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Measuring pH:•pH indicator is a substance which changes color around a particular pH Eg. Litmus paper.•Universal indicator is a mixture of indicators such that it changes color over a range of pH (Thymol blue, phenolpthalein, bromophenol blue etc).•pH meter is used in laboratory.

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Learning Check!

• If the [H+] of a solution is 0.1M, What is the [OH-]? What is the pH?

• What is the difference in [H+] between solution at pH 4 and pH 7?– 3M– 1000-fold difference in [H+]– 3-fold difference in [H+]– 11M

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• pH in biological system:-catalytic activity of enzymes.-blood pH changes can be life-

threatning. pH blood is 7.4.

-acidosis.-alkalosis.

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ACIDS AND BASES-ACIDS AND BASES-STRENGTHSTRENGTH

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• Because strong acids completely ionize, the [H+] of a solution made with a strong acid is easily figured out, since it is equal to the molarity of the solution.

ACIDS AND BASES-ACIDS AND BASES-STRENGTHSTRENGTH

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Learning Check!

• Write out the acid dissociation reaction for hydrochloric acid?

• Calculate the pH of a solution of 5.0 X 10-4 M HCl?

• Write out the acid dissociation reaction for Sodiaum hydroxide?

• Calculate the pH of a solution of 7.0 X 10-5 M NaOH?

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ACIDS AND BASES-ACIDS AND BASES-STRENGTHSTRENGTH

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ACIDS AND BASES-ACIDS AND BASES-STRENGTHSTRENGTH

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ACIDS AND BASES-ACIDS AND BASES-STRENGTHSTRENGTH

• The tendency of any acid to lose proton and form its conjugate base in water is defined by the equilibrium constant (Keq) for reversible reaction:

HA H+ + A-

Keq = [H+] [A-] = Ka

[HA]

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ACIDS AND BASES-ACIDS AND BASES-STRENGTHSTRENGTH

• The degree of dissociation of a weak acid in water is described by the acid dissociation constant, Ka. It is also called the ionization constant.As seen in the figure.

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ACIDS AND BASES-ACIDS AND BASES-STRENGTHSTRENGTH

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ACIDS AND BASES-ACIDS AND BASES-STRENGTHSTRENGTH

• Also included in the figure is pKa which is analogous to pH

pKa = log 1/Ka = -logKa

eg. Ka of acetic acid is 1.74 x 10–5.

pKa = –log (1.74 x 10–5) = 4.76.

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• Experimental determination of amount of acid in a given solution is done by titration. It also reveals the pKa.

• Concentration of the acid in original solution can be calculated from volume and concentration of NaOH added.

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ACIDS AND BASES-ACIDS AND BASES-STRENGTHSTRENGTH

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ACIDS AND BASES-ACIDS AND BASES-STRENGTHSTRENGTH

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ACIDS AND BASES-ACIDS AND BASES-STRENGTHSTRENGTH

• The stronger the acid, the lower its pKa; the stronger the base the higher its pKa.

• pKa can be determined experimentally ; it is the pH at the midpoint of a titration curve for the acid and base.

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Learning Check!

• Which of the following aqueous solutions has the lowest pH: 0.1 M HCl; 0.1 M acetic acid (pKa = 4.86); 0.1 M formic acid (pKa = 3.75)?

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BufferBuffer

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BUFFER

• Buffers are aqueous systems that tend to resist changes in pH when small amounts of acid (H+) or base (OH-) are added.

• A buffer system consists of weak acid (proton donor) and its conjugate base (proton acceptor).

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BufferBuffer

The acetic acid-acetate pair as a buffer system

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Buffers

Buffering regionThis is the zone in the titration curve of a weak acid which extends 1 pH unit on either side of the pKa. In this zone additon of small amount of either H+ or OH- has much less effect on pH than region outside this zone.

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THE HENDERSON–HASSELBALCH EQUATION

• The extent of ionization of a weak acid (the pKa) influences the final concentration of H+ ions (the pH) of the solution, there must be a relationship between pH and the pKa of a weak acid. This relationship is given by the Henderson–Hasselbalch equation:

pH  =  pKa  +  log [conjugate base][acid]

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THE HENDERSON–HASSELBALCH EQUATION

• Calculate pKa, given pH and the molar ratio of proton donor and acceptor;

• Calculate pH, given pKa and the molar ratio of proton donor and acceptor; and

• Calculate the molar ratio of proton donor and acceptor , given pKa and pH.

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Learning check!

• Which of the following compounds would be the best buffer at pH 5.0: formic acid (pKa = 3.8), acetic acid (pKa=4.76) or ethylamine (pka=9.0)?

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Learning check!

(a) What is the pH of a mixture of 0.042 M NaH2PO4 and 0.058 M Na2HPO4?

(b) If 1.0 ml of 10.0N NaOH is added to a liter of the buffer prepared in (a), how much will the pH change?(c) If 1.0 ml of 10.0 N NaOH is added to a liter of pure water at pH 7.0, what is the final pH? Compare with (c)?

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Buffers in cells and tissues

Cytoplasm of cells contain many amino acids with functional groups that are weak acids or weak bases

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Buffers in cells and tissues

Blood plasma is buffered inpart by the bicarbonate system.

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