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E. Chemical Systems and Equilibrium · Acid-Base and Solubility Equilibria

Acid-Base and Solubility Equilibria in Our Bodies, Environment and Industry

E1.2 E3.8 E2.1 A1.9 A2.1About 70 minutes
Learning goals
  • I can explain how the carbonic acid-hydrogen carbonate buffer keeps blood pH within a narrow range.
  • I can describe how equilibria affect hemoglobin, tooth enamel and kidney stones.
  • I can assess the impact of acid-base and solubility equilibria on lakes, oceans and the treatment of contaminated water.
  • I can use calculations from this unit to support an argument about an environmental or technological issue.

Words to know

acidosis / alkalosis
Conditions in which blood pH falls below about 7.35 (acidosis) or rises above about 7.45 (alkalosis).
ocean acidification
The decrease in ocean pH caused by the ocean absorbing CO₂ from the atmosphere.
buffering capacity of a lake
The ability of a lake's water and surrounding rock and soil to neutralize added acid, mainly through carbonate and hydrogen carbonate ions.
hydroxyapatite
Ca₅(PO₄)₃OH, the slightly soluble mineral that makes up most of tooth enamel.
remediation
Cleaning up contaminated water or soil, for example by precipitating dissolved metal ions as insoluble solids.

Equilibrium is everywhere

Right now your blood is holding its pH between about 7.35 and 7.45 while your muscles make acid and your lungs breathe out CO₂. The ocean is absorbing about a quarter of the CO₂ that people release into the air each year. In Northern Ontario, many lakes near Sudbury that were damaged by acid rain have been recovering since smelter emissions were cut. All of these depend on the equilibria from this unit: Ka, buffers, Ksp and Le Châtelier's principle. In Equilibrium in Living Things, the Environment and Technology (unit Chemical Equilibrium) you explained several of these systems qualitatively with Le Châtelier's principle. This lesson adds the numbers from this unit (pH, buffer ratios and Ksp) and is about assessing their impact: using chemistry to explain real systems and to judge claims and decisions about them.

1. The blood buffer

The main buffer in blood plasma is the carbonic acid-hydrogen carbonate system:

CO₂(aq) + H₂O(l) ⇌ H₂CO₃(aq) ⇌ H⁺(aq) + HCO₃⁻(aq)

At body temperature, with dissolved CO₂ counted as the acid, the effective pKa is about 6.1. Normal blood has [HCO₃⁻] ≈ 24 mmol/L and dissolved CO₂ ≈ 1.2 mmol/L, a ratio of 20 : 1:

pH = 6.1 + log(24 ÷ 1.2) = 6.1 + log 20 = 7.4

That pH is more than one unit above pKa, so on paper this is a lopsided buffer. It works so well because the body controls both partners: the lungs remove CO₂ (within minutes) and the kidneys adjust HCO₃⁻ and excrete H⁺ (over hours to days). When exercise floods the blood with acid, the HCO₃⁻ absorbs it, and faster breathing removes the extra CO₂, shifting the equilibria to the left.

If breathing is too slow (for example during some lung diseases), CO₂ builds up, the equilibria shift right and pH falls (respiratory acidosis). Breathing too fast (hyperventilating) removes too much CO₂, and pH rises (respiratory alkalosis). Phosphate (H₂PO₄⁻/HPO₄²⁻) and proteins act as buffers too, especially inside cells.

CO₂(aq)+H₂OH₂CO₃H⁺+HCO₃⁻LUNGSbreathing out CO₂shifts equilibria left,using up H⁺KIDNEYSkidneys keep orexcrete HCO₃⁻ andexcrete H⁺Normal blood pH: 7.35 to 7.45, with [HCO₃⁻] : [CO₂] about 20 : 1
The blood buffer is an open system. The lungs control the CO₂ end of the equilibrium and the kidneys control the HCO₃⁻ end.
Worked example

Example 1: When CO₂ builds up

A patient's breathing slows, and dissolved CO₂ in the blood rises from 1.2 to 1.8 mmol/L while [HCO₃⁻] stays at 24 mmol/L. Estimate the new blood pH (pKa = 6.1). Is the patient in acidosis?

  1. pH = pKa + log([HCO₃⁻] ÷ [CO₂]) = 6.1 + log(24 ÷ 1.8).
  2. 24 ÷ 1.8 = 13.3; log 13.3 = 1.12.
  3. pH = 6.1 + 1.12 = 7.22.

pH ≈ 7.2, below 7.35: respiratory acidosis. Respiratory therapists and physicians measure exactly these values ("blood gases") to diagnose breathing problems.

2. Hemoglobin, teeth and kidney stones

Hemoglobin (recap). You studied Hb + O₂ ⇌ HbO₂, altitude and carbon monoxide in Equilibrium in Living Things, the Environment and Technology. The acid-base link is new here: muscles produce CO₂ and H⁺, and a lower pH makes hemoglobin release O₂ more readily (the Bohr effect), so oxygen goes where it is needed most. The blood buffer above keeps that pH change small everywhere else.

Tooth enamel. As you saw in Chemical Equilibrium, enamel is mostly hydroxyapatite:

Ca₅(PO₄)₃OH(s) ⇌ 5 Ca²⁺(aq) + 3 PO₄³⁻(aq) + OH⁻(aq)

When bacteria in plaque ferment sugars, they make acids. H₃O⁺ removes OH⁻ and PO₄³⁻ (both are bases), so the equilibrium shifts right and enamel dissolves (demineralization). Saliva, a buffer containing HCO₃⁻ and phosphate, raises the pH again so minerals can re-deposit. Fluoride replaces OH⁻ to form fluorapatite, Ca₅(PO₄)₃F, which is less soluble in acid; F⁻ is a much weaker base than OH⁻.

Kidney stones. The most common kind is calcium oxalate (Ksp ≈ 2.3 × 10⁻⁹). When urine becomes concentrated (for example with too little water intake), the ion product of Ca²⁺ and oxalate can exceed Ksp, and crystals can form and grow. Drinking more water lowers both concentrations, and therefore Q.

3. Lakes, acid rain and the Canadian Shield

Burning fossil fuels and smelting sulfide ores release SO₂ and NOₓ, which form sulfuric and nitric acids in the atmosphere. Normal rain has a pH of about 5.6 (from dissolved CO₂); acid rain is lower.

What happens next depends on buffering capacity. Lakes in areas with limestone (CaCO₃) contain plenty of HCO₃⁻ and CO₃²⁻, which neutralize added acid. Many lakes on the Canadian Shield, which covers much of Northern Ontario, sit on granite and other rocks that dissolve very little, so they have little HCO₃⁻ and are easily acidified. As the pH of a lake falls, fish and other organisms are harmed, and aluminium leached from soil (its compounds are more soluble in acid) adds to the damage.

Around Sudbury, decades of smelter emissions acidified many lakes and damaged the surrounding land. In 1960 the Sudbury smelters were the largest single source of sulfur emissions in the world, and an estimated 7000 lakes in the region were damaged by acid. Since then, SO₂ and metal emissions have been cut by more than 90 % (through smelter controls such as acid plants and process changes), and many lakes have recovered chemically, with fish such as lake trout returning. Recovery is not complete: calcium loss from soils, climate change and other stresses slow it in some lakes. The Sudbury regreening program spread crushed limestone on acidic, barren soils so that plants could grow again: an acid-base reaction (CaCO₃ + 2 H₃O⁺ → Ca²⁺ + CO₂ + 3 H₂O) used on a landscape scale.

4. Ocean acidification

The ocean absorbs CO₂, which forms carbonic acid. The average pH of surface seawater has dropped from about 8.2 before industrialization to about 8.05 today (8.04 in 2024), often rounded to "about 8.1". That sounds small, but it is a logarithmic scale: [H₃O⁺] has risen by about 30%. In 2025, scientists assessing Earth's "planetary boundaries" reported that ocean acidification has moved past its proposed safe limit. The extra H⁺ combines with carbonate ions, lowering [CO₃²⁻]. Corals, oysters, mussels, pteropods and many plankton build shells and skeletons of CaCO₃, which becomes harder to build and easier to dissolve when [CO₃²⁻] falls.

CO₂ in the airCO₂(aq)+H₂OH₂CO₃H⁺+HCO₃⁻The extra H⁺ reacts with carbonate ions:H⁺+CO₃²⁻HCO₃⁻Less CO₃²⁻ means Q for CaCO₃(s) ⇌ Ca²⁺ + CO₃²⁻ falls:shells and corals are harder to build and easier to dissolve.ocean surface water
How CO₂ from the air lowers ocean pH and removes the carbonate ions that shell-building organisms need. Each step is an equilibrium you have studied in this unit.

5. Cleaning up water with Ksp

Acid mine drainage forms when sulfide minerals exposed by mining react with air and water, making acidic water rich in dissolved metal ions. A common treatment is to add lime (Ca(OH)₂ or CaO). Raising the pH neutralizes the acid and pushes Q above Ksp for metal hydroxides such as Fe(OH)₃ and Cu(OH)₂, so the metals precipitate and can be settled out as sludge. Treatment plants choose the pH carefully, because each metal hydroxide precipitates over a different pH range (and some, such as aluminium hydroxide, redissolve if the pH goes too high).

Other examples from industry and medicine:

  • Water softening: hard water contains Ca²⁺ and Mg²⁺. Adding lime and sodium carbonate precipitates CaCO₃ and Mg(OH)₂.
  • Medical imaging: BaSO₄ is so slightly soluble that a patient can drink a suspension of it before an X-ray; very little toxic Ba²⁺ dissolves.
  • Swimming pools: operators keep pH near 7.2 to 7.8, using buffers and acids or bases, so that chlorine disinfects well and CaCO₃ scale does not form.

Careers that use this unit: respiratory therapist, nurse, physician, dentist and dental hygienist, pharmacist, water and wastewater treatment operator, environmental technologist, chemical engineer, mining engineer, oceanographer and food scientist.

Worked example

Example 2: How much limestone for a lake?

A small Canadian Shield lake holds 1.0 × 10⁹ L of water at pH 4.5. Estimate the mass of CaCO₃ needed to raise it to pH 6.5, considering only the H₃O⁺ already in the water. CaCO₃ + 2 H₃O⁺ → Ca²⁺ + CO₂ + 3 H₂O.

  1. [H₃O⁺] at pH 4.5 = 3.16 × 10⁻⁵ mol/L; at pH 6.5 = 3.2 × 10⁻⁷ mol/L.
  2. H₃O⁺ to remove = 3.16 × 10⁻⁵ − 0.03 × 10⁻⁵ = 3.13 × 10⁻⁵ mol/L.
  3. Total moles = 3.13 × 10⁻⁵ × 1.0 × 10⁹ = 3.1 × 10⁴ mol of H₃O⁺.
  4. n(CaCO₃) = 3.1 × 10⁴ ÷ 2 = 1.57 × 10⁴ mol; mass = 1.57 × 10⁴ × 100.09 g = 1.6 × 10⁶ g.

About 1.6 tonnes of CaCO₃ as a minimum. In practice much more is needed, because acid keeps arriving in rain and runoff and acidic soils around the lake also consume it: liming treats the symptom, while cutting emissions treats the cause.

Worked example

Example 3: Removing copper from mine water

Mine water is treated with lime until the pH is 8.0. What is the highest concentration of Cu²⁺ that can remain dissolved? (Ksp of Cu(OH)₂ = 2.2 × 10⁻²⁰; M(Cu) = 63.55 g/mol)

  1. At pH 8.0, pOH = 6.0, so [OH⁻] = 1.0 × 10⁻⁶ mol/L.
  2. At saturation, [Cu²⁺] = Ksp ÷ [OH⁻]² = 2.2 × 10⁻²⁰ ÷ (1.0 × 10⁻⁶)² = 2.2 × 10⁻⁸ mol/L.
  3. In mass: 2.2 × 10⁻⁸ × 63.55 = 1.4 × 10⁻⁶ g/L = 1.4 µg/L.

At most about 2.2 × 10⁻⁸ mol/L (1.4 µg/L) of copper stays dissolved. (Real values can be higher, because some Cu²⁺ forms soluble complexes; operators check with lab tests.)

Just for fun

Before some X-rays, patients drink a chalky "barium milkshake" of BaSO₄. It doesn't win any taste awards, but thanks to a Ksp of about 1 × 10⁻¹⁰, almost none of the barium dissolves, so the drink is safe and the X-ray picture comes out sharp.

Hands-on activity

Breath, buffers and shells: a kitchen model of ocean acidification

You need: red cabbage indicator, 2 clear glasses, a drinking straw for each person, baking soda, white vinegar, and a clean eggshell (or a piece of white chalk, which is often calcium carbonate or calcium sulfate; eggshell works better).

Grown-up note: supervise the indicator preparation (knife, hot water). When using the straw, blow out only, never sip, and use a fresh straw for each person.

  1. Glass A: ½ cup of water + 3 tablespoons of indicator. Glass B: the same, plus a small pinch of baking soda (it should turn bluish).
  2. Blow gently through a straw into glass A for 1 to 2 minutes. Watch the colour. Then do the same for glass B and compare.
  3. Explain: CO₂ from your breath forms carbonic acid in the water. Which glass is like a poorly buffered Canadian Shield lake, and which is like the ocean or a limestone lake?
  4. Put a piece of eggshell in a small glass of vinegar and watch it for a few minutes, then leave it overnight. Write the equation for the reaction. (Vinegar is far more acidic than seawater, so this exaggerates the effect: it shows the direction of the change, not its speed in the ocean.)

What to look for: glass A slowly shifts from purple toward pink-purple as CO₂ dissolves. Glass B stays bluish much longer, because HCO₃⁻ absorbs the acid (its buffering capacity). The eggshell fizzes: CaCO₃(s) + 2 CH₃COOH(aq) → Ca²⁺(aq) + 2 CH₃COO⁻(aq) + H₂O(l) + CO₂(g), and becomes thin and soft. Acid shifts the CaCO₃ dissolving equilibrium to the right by removing CO₃²⁻.

Your turn

1

Write the equilibria that make up the blood's main buffer system.

2

During hard exercise, lactic acid enters the blood. Explain how the blood buffer and the lungs respond.

3

Find the blood pH if [HCO₃⁻] = 24 mmol/L and dissolved CO₂ = 0.80 mmol/L (pKa 6.1). What condition is this?

4

Explain, using Le Châtelier's principle, why acids produced by plaque bacteria damage tooth enamel.

5

Why are many lakes on the Canadian Shield more harmed by acid rain than lakes in limestone areas?

6

Ocean surface pH fell from about 8.2 to about 8.1. By what factor did [H₃O⁺] increase?

More practice: warm-up

1

What is the normal pH range of human blood?

2

Which organ removes CO₂ from the blood?

3

What mineral is tooth enamel mostly made of?

4

Name one substance added to acidic lakes or soils to neutralize them.

5

Why is BaSO₄ safe to drink for X-rays, even though Ba²⁺ is toxic?

More practice: on your own

1

Explain the Bohr effect in terms of equilibrium, and why it is useful.

2

A home has a gas furnace. Use equilibrium ideas to explain why a carbon monoxide alarm is important.

3

Explain why fluoride makes enamel more resistant to acid.

4

Mine water at pH 3 contains dissolved Fe³⁺. Use Ksp to explain why adding lime removes the iron.

5

A student claims that "a drop of 0.1 in ocean pH is too small to matter." Evaluate the claim using chemistry from this unit.

Challenge

1

Why does the blood buffer work so well even though its pKa (6.1) is more than one unit below blood pH (7.4)?

2

Use Ksp (2.3 × 10⁻⁹) to find the largest [C₂O₄²⁻] that can stay dissolved in a solution with [Ca²⁺] = 2.5 × 10⁻³ mol/L. Explain how drinking more water helps prevent calcium oxalate stones.

3

Write a short argument (4 to 6 sentences) assessing whether liming is a good long-term solution for acidified lakes. Use at least two calculations or equilibria from this unit.

Check your understanding

Quiz

1.

What happens to blood pH if a person hyperventilates (breathes too fast)?

2.

Why are lakes in limestone regions less affected by acid rain?

3.

How does fluoride protect teeth?

4.

How does adding lime to acid mine drainage remove dissolved metals?

5.

Ocean acidification makes it harder for oysters to build shells mainly because

6.

A blood sample has [HCO₃⁻] = 24 mmol/L and dissolved CO₂ = 1.2 mmol/L (pKa 6.1). What is its pH?

For parents and teachers

Big idea (E1.2): the equilibria in this unit control real systems. The CO₂/HCO₃⁻ buffer, managed by the lungs and kidneys, keeps blood pH near 7.4. Acid shifts the solubility equilibria of tooth enamel and shells. Buffering capacity decides how much acid rain harms a lake, and Ksp lets engineers remove toxic metals from water.

How to help: Discuss a current news story about acid rain recovery, ocean acidification or water treatment, and ask your teen to explain the chemistry behind it using one equation from this unit. The breath activity is safe and quick; make sure everyone blows out (never sips) and uses their own straw. The Challenge argument question is like an exam essay question; look for chemistry evidence and a clear judgment.

Common difficulties:

  • Treating the blood buffer like a closed beaker and forgetting the lungs and kidneys.
  • Underestimating small pH changes: 0.1 pH unit is about a 26% change in [H₃O⁺].
  • Thinking liming cures acidification permanently; the acid source must also be reduced.
  • Mixing up which ion is removed by acid (OH⁻, CO₃²⁻ and PO₄³⁻ are bases; Cl⁻ is not).