Aqueous ions and concentration: keep amount and volume separate

MCAT content library / Chemistry & physics / Aqueous ions and concentration: keep amount and volume separate

Track each species in moles before dividing by the final volume. Use dissociation coefficients and charge balance to check the result.

About 14 minutes, including the worked examples and checks.

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Concept: a dissolved amount is not yet a concentration

A solution calculation has two separate questions: what chemical species are present, and how much solution contains them? AAMC category 5A includes dissolved ions, hydration, hydronium, and concentration units.1 Keeping species, amount, and final volume in separate columns prevents several different errors from producing the same plausible-looking number.

An aqueous ion is surrounded by water molecules. Water’s polarity allows ion–dipole attractions that help stabilize separated ions. When a soluble ionic compound dissociates, its formula determines the relative amounts of cations and anions. A strong electrolyte produces ions essentially completely under the stated solution conditions; a dissolved molecular substance may remain uncharged or react only partly to form ions.2

For a fully dissociated calcium chloride solution, write CaCl2 → Ca2+ + 2 Cl−. One mole of dissolved formula units supplies one mole of calcium ions and two moles of chloride ions. The subscript two belongs to chloride’s count; the superscript 2+ belongs to calcium’s charge. They perform different jobs.

Likewise, the polyatomic ion NH4+ has one positive charge on the whole ammonium ion. It is not four separate hydrogen ions. H3O+, hydronium, represents a proton associated with water. In introductory aqueous equations, H+ is often shorthand for this hydrated proton rather than an isolated bare proton in solution.3

Pattern: read the denominator as carefully as the solute

Molarity is amount of solute divided by final solution volume: c = n/V, with n in mol and V in L. Thus 0.100 mol in 0.500 L is 0.200 mol/L, written 0.200 M. The denominator is not the volume of water initially poured into the flask. Dissolving a solid or mixing liquids can change the final volume.4

Unit or labelMeaningInformation needed for conversion
mol/L, or MMoles of stated solute per liter of solutionSpecies identity and final solution volume
g/LGrams of stated solute per liter of solutionMolar mass to convert to mol/L
% by massGrams of solute per 100 g of solutionSolution density to connect mass and volume
% mass/volumeGrams of solute per 100 mL of solutionThe explicit mass/volume convention
Concentration units describe different ratios

For example, 5.85 g/L of NaCl is 0.100 mol/L when its supplied molar mass is 58.5 g/mol. A 5.85% mass/volume solution contains 5.85 g per 100 mL, which is ten times as much per liter. “Percent” without a stated basis is incomplete information; mass percent and mass/volume percent need not be numerically equal.5

Application: prepare two solutions, then mix measured portions

The following preparation and mixing data are illustrative. Assume pure anhydrous salts, complete dissolution and dissociation, no precipitation or other reaction, and the stated final volumes. Use CaCl2 = 111 g/mol and NaCl = 58.5 g/mol.

StockPreparationDissolved amountFormula-unit concentration
A: CaCl22.22 g brought to 100.0 mL final volume0.0200 mol0.200 M
B: NaCl1.17 g brought to 200.0 mL final volume0.0200 mol0.100 M
Original stock-solution preparation

The stocks contain the same amount of salt formula units, but stock A has half the volume. Its formula-unit concentration is therefore twice as large. In A, [Ca2+] = 0.200 M and [Cl−] = 0.400 M. In B, both [Na+] and [Cl−] equal 0.100 M. Brackets here indicate the molar concentration of the particular species inside them.

Now combine 50.0 mL of A with 150.0 mL of B. For this example, the measured final volume is 200.0 mL. Calculate each contribution as n = cV before adding it to the common vessel.

IonFrom 50.0 mL AFrom 150.0 mL BTotal divided by 0.2000 L
Ca2+0.0100 mol00.0500 M
Na+00.0150 mol0.0750 M
Cl−0.0200 mol0.0150 mol0.175 M
Amounts entering the mixture and resulting ion concentrations

Chloride has two sources. Adding the original chloride concentrations, 0.400 M + 0.100 M, would incorrectly treat both concentrations as though they referred to the final volume. Even their unweighted average would be wrong because the sampled volumes differ. The general nonreacting mixture relation is cfinal = (cAVA + cBVB)/Vfinal for the same species.

Rule: dilution conserves solute amount; mixing may require more bookkeeping

Suppose 40.0 mL of the mixture is transferred and diluted to 200.0 mL. The transferred portion contains 0.175 mol/L × 0.0400 L = 0.00700 mol of chloride. Dilution leaves that amount unchanged while increasing its volume fivefold, so [Cl−] becomes 0.0350 M. Calcium and sodium concentrations also fall by a factor of five.

The familiar relation c1V1 = c2V2 is this conservation statement written twice. It applies to the amount actually transferred, not automatically to the entire stock bottle. It also assumes no gain, loss, or reaction of the tracked solute during dilution.4

Adding 200 mL of water is different from bringing a sample to 200 mL final volume. If the final volume is not supplied and volume additivity is not justified, an exact concentration cannot be obtained from component volumes alone. The bookkeeping still gives the amount; the missing quantity is the denominator.

Audit the result with charge balance

For the mixture above, positive charge equivalents per liter are 2[Ca2+] + [Na+] = 2(0.0500) + 0.0750 = 0.175. Negative charge equivalents are [Cl−] = 0.175. The charges balance even though there are more chloride ions than calcium and sodium ions combined. Electrical neutrality requires equal total positive and negative charge, not equal numbers of positive and negative ions.

This check can expose a missing coefficient or counterion. It cannot prove that every concentration is correct: multiplying all three concentrations by the same wrong factor would preserve charge balance. Pair it with independent amount and volume checks. If a new mixture precipitates a salt, forms a complex, or transfers protons, first account for that chemistry; the assumption of independently conserved free-ion amounts has then changed.

Check your reasoning

Choose an answer before opening its feedback. Each option explains the reasoning behind that choice.

Check 1

A sample containing 0.00400 mol of MgCl2 is completely dissolved and dissociated in a final volume of 250 mL. No other chloride source or reaction is present. What is [Cl−]?

A. 0.00800 M

Review this choice. This divides the formula-unit concentration by two. Each MgCl₂ formula unit supplies two chloride ions, so the chloride amount is twice the salt amount.

B. 0.0160 M

Review this choice. This is 0.00400 mol/0.250 L, the formula-unit concentration and the magnesium concentration. Chloride has a coefficient of two.

C. 0.0320 M

Correct. The chloride amount is 2 × 0.00400 = 0.00800 mol. Dividing by 0.250 L gives 0.0320 M.

D. 0.0480 M

Review this choice. This is the sum of magnesium and chloride ion concentrations. The question asks for chloride alone, not all dissolved ions.

The principle to carry forward

Specify the ion first, use the dissociation coefficient, and divide by the final solution volume.

Check 2

A 40.0 mL portion of 0.240 M NaCl is diluted with water to a final volume of 200.0 mL. Assume complete dissociation and no reaction or loss. Which pair gives the chloride amount and concentration after dilution?

A. 0.00192 mol; 0.0480 M

Review this choice. The concentration correctly falls fivefold, but the amount does not. The transferred portion still contains 0.240 × 0.0400 = 0.00960 mol chloride.

B. 0.00960 mol; 0.0480 M

Correct. Dilution conserves the transferred 0.00960 mol. Dividing by 0.2000 L gives 0.0480 M.

C. 0.00960 mol; 0.0600 M

Review this choice. The amount is correct, but 0.0600 M results from dividing by 0.160 L, the difference between the two stated volumes. Concentration uses the complete final solution volume.

D. 0.00960 mol; 0.240 M

Review this choice. The amount is unchanged, but its distribution volume has increased fivefold. The original concentration cannot remain unchanged after this dilution.

The principle to carry forward

Dilution changes the concentration of the transferred sample without changing its solute amount.

Check 3

A proposed solution model contains only Na+, Ca2+, and Cl− at appreciable concentrations. Water’s hydronium and hydroxide contributions are negligible on this concentration scale. If [Na+] = 0.040 M and [Ca2+] = 0.030 M, which chloride concentration is consistent with electrical neutrality?

A. 0.035 M

Review this choice. Halving the sum of cation concentrations has no charge-balance basis. Calcium contributes two positive charge equivalents per ion.

B. 0.050 M

Review this choice. This counts too little negative charge. The positive total is 0.040 + 2(0.030) = 0.100 charge equivalents per liter.

C. 0.070 M

Review this choice. This equals the number concentration of cations, but not their charge-weighted total. Calcium is divalent.

D. 0.100 M

Correct. Each chloride contributes one negative charge. Its concentration must equal 0.040 + 2(0.030) = 0.100 M when these are the only appreciable ions.

The principle to carry forward

A charge-balance audit weights each ion concentration by the magnitude of its charge; unequal ion counts can still describe a neutral solution.

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From solutions to buffers

Lesson 2 of 6.

See every step in From solutions to buffers

From solutions to buffers

Build a quantitative acid–base explanation and apply it to amino acid charge.

  1. Moles, formulas, and yield: conserve the reacting material
  2. Aqueous ions and concentration: keep amount and volume separate · You are here
  3. Acid–base strength: distinguish concentration from dissociation
  4. Weak acids, bases, and salts: choose a defensible pH calculation
  5. Buffers: explain pH resistance and its limits
  6. Amino acid and peptide charge: count the groups that can change

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Sources

1. AAMC — Content Category 5A

2. OpenStax Chemistry 2e — Electrolytes

3. OpenStax Chemistry 2e — Brønsted–Lowry Acids and Bases

4. OpenStax Chemistry 2e — Molarity

5. OpenStax Chemistry 2e — Other Units for Solution Concentrations