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Inquiry Question 3: It is all about hydrogen ions

Investigate the application of buffer systems in natural and industrial contexts, including the bicarbonate buffer in blood and the Henderson-Hasselbalch description of buffer pH

A focused answer to the HSC Chemistry Module 6 dot point on buffer applications. Buffer action revisited, the Henderson-Hasselbalch equation, the bicarbonate buffer in blood (HCO3/H2CO3), respiratory and renal compensation, and worked HSC past exam questions.

Reviewed by: AI editorial process; not yet individually human-reviewed

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  1. What this dot point is asking
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What this dot point is asking

NESA wants you to consolidate buffer chemistry by applying it to natural and industrial contexts, especially the bicarbonate buffer in blood, and to use the Henderson-Hasselbalch equation quantitatively. You should be able to write the buffer equilibria, explain the response to added strong acid or base in equation form, and link the chemistry to physiological situations like exercise, hyperventilation, and acidosis. This builds on conjugate acid-base pairs and the Module 5 page on buffer systems.

The answer

Buffer composition and action (recap)

A buffer is a solution containing significant amounts of both a weak acid and its conjugate base (or a weak base and its conjugate acid). The two species sit in equilibrium:

HA(aq)H(aq)++A(aq)HA_{(aq)} \rightleftharpoons H^+_{(aq)} + A^-_{(aq)}

Response to added strong acid (extra H+H^+). The conjugate base consumes it:

A(aq)+H(aq)+HA(aq)A^-_{(aq)} + H^+_{(aq)} \rightarrow HA_{(aq)}

Response to added strong base (extra OHOH^-). The weak acid consumes it:

HA(aq)+OH(aq)A(aq)+H2O(l)HA_{(aq)} + OH^-_{(aq)} \rightarrow A^-_{(aq)} + H_2O_{(l)}

In each case, the strong reagent is converted into the corresponding member of the conjugate pair, so [H+][H^+] moves only slightly. The buffer fails when one component is essentially exhausted.

The Henderson-Hasselbalch equation

Take logarithms of the KaK_a expression:

Ka=[H+][A][HA]pH=pKa+log10([A][HA])K_a = \frac{[H^+][A^-]}{[HA]} \quad \Rightarrow \quad pH = pK_a + \log_{10}\left(\frac{[A^-]}{[HA]}\right)

This is the Henderson-Hasselbalch equation. Three quick consequences:

  • When [A]=[HA][A^-] = [HA] (equimolar buffer), pH=pKapH = pK_a. Buffer capacity is maximised here.
  • The useful range of a buffer is roughly pKa±1pK_a \pm 1 (corresponding to a 10:1 ratio of components on either side).
  • To make a buffer of a target pH, choose a weak acid with pKapK_a within one unit of the target, then set the ratio.

An owned illustrative buffer-response curve shows why a 20:1 ratio, far from ideal on paper, still keeps blood pH stable in practice: the curve is flattest near pH=pKapH = pK_a, but it is only truly steep once a component is nearly exhausted.

Illustrative buffer-response curve for the bicarbonate system An owned illustrative plot of blood pH against the ratio of bicarbonate to carbonic acid, plotted on a logarithmic ratio axis, for pKa1 equals 6.10. The curve is a shallow S-shape: pH rises slowly with ratio across the buffer region from ratio 0.5 to ratio 30, passing through pH 6.10 at a 1 to 1 ratio, and flags the physiological operating point at ratio 20, pH 7.40. Beyond ratio 50 the curve steepens sharply as the buffer becomes exhausted. 8.1 7.4 6.8 6.1 5.1 ratio 1:1 pH = pKa1 = 6.10 blood operating point ratio 20:1, pH 7.40 0.5 2 20 50 100 Ratio [HCO3-] / [H2CO3] (log scale, illustrative ExamExplained curve) Flattest near pKa1; steepens sharply once one component is nearly exhausted (ratio below 0.2 or above 100).

The bicarbonate buffer in blood

Arterial blood is maintained at pH 7.40±0.057.40 \pm 0.05 by a coupled buffer-respiratory-renal system. The dominant chemical buffer is the bicarbonate pair:

CO2(g)+H2O(l)H2CO3(aq)H(aq)++HCO3(aq)CO_{2(g)} + H_2O_{(l)} \rightleftharpoons H_2CO_{3(aq)} \rightleftharpoons H^+_{(aq)} + HCO_{3(aq)}^-

For this system pKa1=6.10pK_{a1} = 6.10 at body temperature, with typical concentrations [HCO3]24[HCO_3^-] \approx 24 mmol/L and [H2CO3]1.2[H_2CO_3] \approx 1.2 mmol/L (in equilibrium with dissolved CO2CO_2).

pH=6.10+log10(241.2)=6.10+1.30=7.40pH = 6.10 + \log_{10}\left(\frac{24}{1.2}\right) = 6.10 + 1.30 = 7.40

The ratio is far from 1:1, so chemically this is a poor buffer in isolation. What makes it physiologically powerful is that both components are continuously regulated:

  • [H2CO3][H_2CO_3] is controlled by breathing rate (the lungs expel CO2CO_2).
  • [HCO3][HCO_3^-] is controlled by the kidneys (which excrete or retain bicarbonate).

This "open" buffer can therefore reset its components in response to disturbances, something a closed buffer in a beaker cannot do.

The bicarbonate buffer as an open system regulated by lungs and kidneys A schematic reaction scheme showing carbon dioxide gas plus water in equilibrium with carbonic acid, which is in equilibrium with hydrogen ion plus bicarbonate ion. The lungs, on the left, control carbon dioxide and hence carbonic acid within minutes by adjusting breathing rate. The kidneys, on the right, control bicarbonate ion within hours to days by excreting or reabsorbing it. Because both ends of the equilibrium can be independently reset, the open buffer restores the 20 to 1 bicarbonate to carbonic acid ratio even after a large disturbance. Lungs breathing rate sets CO2, minutes CO2 + H2O H2CO3 H+ + HCO3- Kidneys excrete or retain HCO3-, hours to days Fast lever adjusts [H2CO3] side Slow lever adjusts [HCO3-] side Two independent gates restore the 20:1 ratio after a disturbance An "open" buffer resupplies both sides; a closed beaker buffer cannot regenerate a consumed component.

Acid-base disturbances

Condition Cause What happens to pH Compensation
Respiratory acidosis Hypoventilation (slow breathing, COPD): CO2CO_2 accumulates falls Kidneys retain HCO3HCO_3^-
Respiratory alkalosis Hyperventilation (panic, altitude): CO2CO_2 exhaled too fast rises Kidneys excrete HCO3HCO_3^-
Metabolic acidosis Excess acid (uncontrolled diabetes, lactic acid build-up) falls Lungs increase ventilation to expel CO2CO_2
Metabolic alkalosis Excess base (vomiting, certain antacids) rises Lungs reduce ventilation, retain CO2CO_2

In each case the body shifts the bicarbonate equilibrium to restore the 20:1 ratio.

Other physiological buffers

  • Phosphate buffer (H2PO4H_2PO_4^-/HPO42HPO_4^{2-}): pKa=7.20pK_a = 7.20. Important inside cells where bicarbonate is less effective. Also the basis for laboratory buffers (PBS).
  • Protein buffers (haemoglobin in particular): histidine side chains have pKapK_a near 6, so they buffer near physiological pH. Haemoglobin doubles as the oxygen carrier and a major intracellular buffer.

Industrial and laboratory buffers

Buffer pKapK_a Useful range Typical use
Citric acid / citrate 3.13, 4.76, 6.40 2 to 7 Food, soft drinks
Acetate (ethanoate) 4.76 3.7 to 5.7 Enzyme assays, electroplating
Carbonate (HCO3/CO3) 10.33 9.3 to 11.3 Cleaning products
Phosphate (H2PO4/HPO4) 7.20 6.2 to 8.2 Biological PBS
Tris 8.07 7.0 to 9.0 Molecular biology

Examples in context

Example 1. Diabetic ketoacidosis presentation at Westmead ED. A 16-year-old with type-1 diabetes presents at Westmead emergency with rapid breathing and confusion. Arterial blood gases show pH 7.10, [HCO3][HCO_3^-] at 8 mmol L1^{-1} and pCO2pCO_2 at 18 mmHg. Plugging into Henderson-Hasselbalch with pKa=6.1pK_a = 6.1, pH=6.1+log(8/(0.03×18))=6.1+1.17=7.27pH = 6.1 + \log(8 / (0.03 \times 18)) = 6.1 + 1.17 = 7.27, just above the patient's measured value, reflecting partial respiratory compensation. The patient's body is hyperventilating to blow off CO2CO_2 and raise the ratio, but renal bicarbonate reserves are exhausted by ketoacid load. Treatment with intravenous saline plus insulin restores the ratio over 8 to 12 hours.

Example 2. Aquaculture water buffering at the Port Stephens prawn farm. Black Tiger prawn larvae from NSW DPI hatcheries require pond water held at pH 8.0 to 8.3. Operators buffer ponds with a sodium carbonate / sodium bicarbonate system, the CO32CO_3^{2-} / HCO3HCO_3^- pair with pKapK_a near 10.3. The Henderson-Hasselbalch ratio at pH 8.2 is therefore 108.210.3=102.1=0.007910^{8.2 - 10.3} = 10^{-2.1} = 0.0079, so [HCO3][HCO_3^-] overwhelms [CO32][CO_3^{2-}]. Adding 50 g of Na2CO3Na_2CO_3 per 1000 L raises buffering capacity without spiking pH. Without the buffer, algal photosynthesis during the day would push pond pH above 9.0 and dissolve larval shells.

Try this

Q1. State the Henderson-Hasselbalch equation and explain what it predicts for a buffer with equal concentrations of weak acid and conjugate base. [3 marks]

  • Cue. pH=pKa+log([A]/[HA])pH = pK_a + \log([A^-] / [HA]); when concentrations are equal the log is 0 and pH=pKapH = pK_a.

Q2. Calculate the volume of 0.10 mol L1^{-1} HCl that can be added to 250 mL of a phosphate buffer (containing 0.050 mol HPO42HPO_4^{2-} and 0.050 mol H2PO4H_2PO_4^-) before the pH drops by more than 0.1 unit. [3 marks]

  • Cue. Use Henderson-Hasselbalch: the ratio change log(0.045/0.055)=0.087\log(0.045/0.055) = -0.087, so adding about 0.005 mol HCl corresponds to 50 mL of 0.10 mol L1^{-1} HCl.

Q3. Describe the bicarbonate buffer system and its compensation mechanisms. (a) Write the buffer equilibrium. (b) Explain respiratory compensation. (c) Explain renal compensation. [1+2+2 marks]

  • Cue. (a) H2CO3H++HCO3H_2CO_3 \rightleftharpoons H^+ + HCO_3^-. (b) Breathing rate adjusts CO2CO_2 and hence H2CO3H_2CO_3 within minutes. (c) Kidneys reabsorb or excrete HCO3HCO_3^- over hours to days.

Exam-style practice questions

Practice questions written in the style of NESA exam questions on this dot point, with worked answer explainers. The year tag is the paper they imitate, not the source.

2022 HSC5 marksThe bicarbonate buffer in human blood is described by the equilibrium CO2(g) + H2O(l) <-> H2CO3(aq) <-> H+(aq) + HCO3-(aq). Normal arterial blood has pH 7.40, [HCO3-] = 24 mmol/L, and dissolved [H2CO3] = 1.2 mmol/L. (a) Verify the pH using the Henderson-Hasselbalch equation, given pKa1 of carbonic acid = 6.10 at body temperature. (b) Explain what happens to the equilibrium when CO2 is exhaled more rapidly (hyperventilation), and how this affects blood pH.
Show worked answer →

A 5 mark answer needs the Henderson-Hasselbalch verification, the Le Chatelier shift on hyperventilation, and the pH consequence with direction.

(a) pH from Henderson-Hasselbalch.

pH=pKa+log10([HCO3][H2CO3])=6.10+log10(241.2)=6.10+log10(20)=6.10+1.30=7.40pH = pK_a + \log_{10}\left(\frac{[HCO_3^-]}{[H_2CO_3]}\right) = 6.10 + \log_{10}\left(\frac{24}{1.2}\right) = 6.10 + \log_{10}(20) = 6.10 + 1.30 = 7.40

The calculated pH matches the measured arterial pH.

(b) Hyperventilation. Exhaling CO2CO_2 faster removes the leftmost species in the equilibrium chain. By Le Chatelier, the equilibrium shifts left to replace CO2CO_2, consuming H2CO3H_2CO_3 and (via the second step) consuming H+H^+ from HCO3HCO_3^-. The ratio [HCO3]/[H2CO3][HCO_3^-]/[H_2CO_3] rises, so pH rises.

Quantitatively, if [H2CO3][H_2CO_3] falls to 0.8 mmol/L while [HCO3][HCO_3^-] stays near 24 mmol/L momentarily, pH=6.10+log10(30)=7.58pH = 6.10 + \log_{10}(30) = 7.58. This is respiratory alkalosis, a condition seen in panic attacks and at high altitude.

Markers reward (1) substitution into Henderson-Hasselbalch with correct logarithm, (2) the Le Chatelier shift on exhaling, (3) the direction of pH change with naming of alkalosis.

2018 HSC3 marksExplain how a buffer made from 0.10 mol/L ethanoic acid and 0.10 mol/L sodium ethanoate resists a small addition of strong acid. Include a balanced equation.
Show worked answer →

A buffer contains a weak acid (CH3COOHCH_3COOH) and its conjugate base (CH3COOCH_3COO^-) in comparable amounts.

When a small amount of strong acid (H+H^+) is added, the added H+H^+ is consumed by the conjugate base:

CH3COO(aq)+H(aq)+CH3COOH(aq)CH_3COO^-_{(aq)} + H^+_{(aq)} \rightarrow CH_3COOH_{(aq)}

The strong acid is converted to a weak acid, which only partly re-ionises. The added H+H^+ is therefore not all "free" in solution; most of it has been mopped up. The ratio [CH3COO]/[CH3COOH][CH_3COO^-]/[CH_3COOH] shifts slightly toward the acid side, so pH falls only marginally.

Markers reward (1) the correct weak-acid plus conjugate-base composition, (2) the reaction consuming added H+H^+, (3) explaining that the strong acid is replaced by a much weaker one, so pH changes little.

Practice questions

Original practice questions graded from foundation to exam level, each with a full worked solution. Try them before revealing the solution.

foundation3 marksA 250 mL buffer is prepared from 3.00 g of ethanoic acid (CH3COOHCH_3COOH, M=60.05 g mol1M = 60.05\ \text{g mol}^{-1}, Ka=1.8×105K_a = 1.8 \times 10^{-5}) and 4.10 g of sodium ethanoate (CH3COONaCH_3COONa, M=82.03 g mol1M = 82.03\ \text{g mol}^{-1}). Calculate the pH of the buffer, to 2 decimal places.
Show worked solution →

Step 1: find pKa from Ka.

pKa=log10(1.8×105)=4.74pK_a = -\log_{10}(1.8 \times 10^{-5}) = 4.74

Step 2: moles of each component.

n(CH3COOH)=3.00 g60.05 g mol1=0.04996 moln(CH_3COOH) = \frac{3.00\ \text{g}}{60.05\ \text{g mol}^{-1}} = 0.04996\ \text{mol}

n(CH3COO)=4.10 g82.03 g mol1=0.04998 moln(CH_3COO^-) = \frac{4.10\ \text{g}}{82.03\ \text{g mol}^{-1}} = 0.04998\ \text{mol}

Step 3: ratio of conjugate base to acid. Both are in the same 250 mL volume, so volume cancels and the mole ratio equals the concentration ratio:

[A][HA]=0.049980.04996=1.000\frac{[A^-]}{[HA]} = \frac{0.04998}{0.04996} = 1.000

Step 4: apply Henderson-Hasselbalch.

pH=pKa+log10(1.000)=4.74+0=4.74pH = pK_a + \log_{10}(1.000) = 4.74 + 0 = 4.74

Marking criteria: 1 mark for correctly finding pKa from Ka, 1 mark for correct moles of both components, 1 mark for the correct pH to 2 decimal places (4.74), recognising the near-1:1 ratio makes pH essentially equal to pKa.

foundation3 marksExplain, using an equation, how the bicarbonate buffer resists a small addition of metabolic acid (extra H+H^+) in the blood.
Show worked solution →

The conjugate base of the bicarbonate pair, HCO3HCO_3^-, consumes the added H+H^+:

HCO3(aq)+H(aq)+H2CO3(aq)HCO_{3(aq)}^- + H^+_{(aq)} \rightarrow H_2CO_{3(aq)}

The strong acid's H+H^+ is converted into the weak acid H2CO3H_2CO_3, which only partly re-ionises, so free [H+][H^+] rises only slightly and pH falls only marginally rather than sharply.

Marking criteria: 1 mark for identifying HCO3HCO_3^- as the component that reacts, 1 mark for a correctly balanced equation, 1 mark for explaining why converting strong acid to a weak acid limits the pH change.

core4 marksThe buffer-response curve below plots blood pH against the ratio [HCO3-]/[H2CO3] on a logarithmic axis, with pKa1 = 6.10. Using the curve, (a) estimate the pH at ratio 1:1, and (b) explain why the curve is much steeper near ratio 100:1 than near ratio 5:1.
Show worked solution →

(a) Reading the curve at ratio 1:1. The curve passes through pH 6.10 at the marked ratio 1:1 point, matching pH=pKa1pH = pK_{a1} exactly (since log10(1)=0\log_{10}(1) = 0).

(b) Why the curve steepens near ratio 100:1. Near ratio 100:1, the weak acid component (H2CO3H_2CO_3) is nearly used up relative to the conjugate base, so the buffer has little capacity left to absorb further base; a small further shift in the ratio produces a much larger change in log10(ratio)\log_{10}(\text{ratio}) and hence in pH. Near ratio 5:1, both components remain present in comparable amounts, so the buffer still has plenty of capacity and the curve stays shallow.

Marking criteria: 1 mark for reading pH = 6.10 (= pKa1) at ratio 1:1, 1 mark for linking this to log10(1)=0\log_{10}(1) = 0, 1 mark for identifying that one component is nearly exhausted near ratio 100:1, 1 mark for explaining this in terms of buffer capacity/the logarithmic relationship rather than just asserting "it gets steeper".

core5 marksA patient in diabetic ketoacidosis has arterial [HCO3-] = 10.0 mmol/L and pCO2 = 24 mmHg, with dissolved [H2CO3] related to pCO2 by [H2CO3] = 0.030 x pCO2 (mmol/L, mmHg). Using pKa1 = 6.10, calculate the predicted arterial pH to 2 decimal places, and state whether this represents acidosis, alkalosis, or normal pH.
Show worked solution →

Step 1: find [H2CO3] from pCO2.

[H2CO3]=0.030×24=0.72 mmol/L[H_2CO_3] = 0.030 \times 24 = 0.72\ \text{mmol/L}

Step 2: apply Henderson-Hasselbalch.

pH=pKa1+log10([HCO3][H2CO3])=6.10+log10(10.00.72)pH = pK_{a1} + \log_{10}\left(\frac{[HCO_3^-]}{[H_2CO_3]}\right) = 6.10 + \log_{10}\left(\frac{10.0}{0.72}\right)

=6.10+log10(13.89)=6.10+1.14=7.24= 6.10 + \log_{10}(13.89) = 6.10 + 1.14 = 7.24

Step 3: classify. Normal arterial pH is 7.40±0.057.40 \pm 0.05 (i.e. 7.35 to 7.45). A calculated pH of 7.24 is below 7.35, so this is acidosis. Since [HCO3-] is low (bicarbonate has been consumed buffering the excess ketoacids), the primary disturbance is metabolic acidosis, with partial respiratory compensation shown by the low pCO2 (hyperventilation blowing off CO2 to raise the ratio back towards normal).

Marking criteria: 1 mark for correctly converting pCO2 to [H2CO3], 1 mark for correct substitution into Henderson-Hasselbalch, 1 mark for the correct pH to 2 decimal places (7.24), 1 mark for correctly classifying this as acidosis against the 7.35 to 7.45 reference range, 1 mark for identifying the metabolic origin with respiratory compensation.

exam6 marksAssess the effectiveness of the bicarbonate buffer system, compared with a simple laboratory acetate buffer, at maintaining a stable pH in the human body during vigorous exercise.
Show worked solution →

This is a 6-mark ASSESS: markers reward a judgement supported by contrasted evidence, not just a description of each buffer.

Band 6 PLAN.

  • Thesis: the bicarbonate buffer is far more effective than a closed acetate buffer for the body because it is an OPEN system, continuously regulated by two independent organs, even though its chemical ratio (20:1) is less favourable on paper than an ideal 1:1 buffer.
  • Chemistry of the challenge: vigorous exercise produces lactic acid and increased CO2 from cellular respiration, both adding H+ (directly, and via the CO2/H2CO3 equilibrium) faster than a fixed-composition buffer could absorb.
  • Acetate buffer (closed): a beaker of ethanoic acid/ethanoate can only absorb H+ until one component is consumed; once used up, it cannot regenerate and pH will fall sharply, per the steep region of a Henderson-Hasselbalch buffer-response curve.
  • Bicarbonate buffer (open): breathing rate increases within seconds to expel excess CO2 (shifting the equilibrium left, consuming H+, restoring the ratio), while the kidneys make a slower, sustained adjustment to HCO3- over hours. This means the "used" component of the buffer is constantly resupplied or removed, unlike a sealed system.
  • Judgement: despite a chemically "worse" 20:1 ratio (further from the ideal 1:1 buffer optimum), the bicarbonate system is more effective in the body specifically because physiological regulation, not the intrinsic chemistry, gives it renewable buffer capacity that a closed acetate buffer cannot match.

Model paragraph (excerpt). Although a 1:1 acetate buffer sits exactly at its pKa and would, in an isolated beaker, resist pH change more efficiently per mole than the 20:1 bicarbonate system, this comparison breaks down under a sustained acid load such as vigorous exercise. A fixed acetate buffer has a finite capacity: once the conjugate base is consumed neutralising incoming H+, no more remains and pH falls steeply, following the sharply increasing region of a Henderson-Hasselbalch buffer-response curve. The bicarbonate buffer avoids this because it is open at both ends of its equilibrium: as lactic acid and CO2 raise [H+], the equilibrium CO2+H2OH2CO3H++HCO3CO_2 + H_2O \rightleftharpoons H_2CO_3 \rightleftharpoons H^+ + HCO_3^- shifts right, but increased ventilation immediately vents the CO2 being generated, preventing H2CO3H_2CO_3 from accumulating, while the kidneys make a slower correction to [HCO3-] over the following hours. The buffer's "capacity" is therefore continuously renewed rather than fixed, which is why blood pH typically changes by only hundredths of a unit during intense exercise despite a large acid load.

Marker's note: top-band answers (1) explicitly contrast OPEN versus CLOSED buffer behaviour rather than just describing each system, (2) use the correct equilibrium and both compensation mechanisms with their characteristic timescales, (3) acknowledge the apparent paradox that a 20:1 ratio is chemically further from ideal than 1:1 yet physiologically more effective, and (4) end with an explicit judgement, not a neutral summary.

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