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Monopotassium Phosphate (KH2PO4): Formula, Dissociation, and pH in Water

What is monopotassium phosphate (KH2PO4), and how does it dissociate and influence pH when dissolved in water?

Subject: General Chemistry Chapter: Acid Base Equilibrium Topic: Solutions of Weak Acids or Bases and Their Salts Answer included
monopotassium phosphate potassium dihydrogen phosphate KH2PO4 dihydrogen phosphate amphiprotic ion phosphoric acid pKa salt hydrolysis phosphate buffer
Accepted answer Answer included

Chemical identity and nomenclature

Monopotassium phosphate is an ionic compound commonly written as KH2PO4. The same substance is widely called potassium dihydrogen phosphate. In water it supplies potassium ions, K+, and the dihydrogen phosphate ion, H2PO4, which belongs to the triprotic phosphoric acid system.

The formula KH2PO4 corresponds to one potassium per phosphate unit with two acidic hydrogens retained. Related salts include K2HPO4 (dipotassium phosphate) and K3PO4 (tripotassium phosphate), which differ in charge state and acid–base behavior.

Composition and molar mass

The molar mass follows directly from atomic composition. Using standard atomic masses (to typical classroom precision):

Element Count Contribution (g/mol)
K 1 \(\approx 39.10\)
H 2 \(\approx 2 \times 1.008 = 2.016\)
P 1 \(\approx 30.97\)
O 4 \(\approx 4 \times 16.00 = 64.00\)

Summation:

\[ M(\mathrm{KH_2PO_4}) \approx 39.10 + 2.016 + 30.97 + 64.00 = 136.086\ \mathrm{g/mol} \approx 136.09\ \mathrm{g/mol} \]

Dissociation in water and electrolyte character

As an ionic salt, monopotassium phosphate dissociates extensively in water:

\[ \mathrm{KH_2PO_4(s) \rightarrow K^+(aq) + H_2PO_4^-(aq)} \]

Potassium, K+, is the spectator cation of a strong base (KOH) and has negligible acid–base influence. The pH behavior is dominated by H2PO4.

Acid–base behavior of the dihydrogen phosphate ion

The dihydrogen phosphate ion is amphiprotic: it can donate a proton to form HPO42− and can accept a proton to form H3PO4. These equilibria connect to the successive dissociations of phosphoric acid:

\[ \mathrm{H_3PO_4 \rightleftharpoons H^+ + H_2PO_4^-} \quad (K_{a1},\ pK_{a1}\approx 2.15) \] \[ \mathrm{H_2PO_4^- \rightleftharpoons H^+ + HPO_4^{2-}} \quad (K_{a2},\ pK_{a2}\approx 7.20) \] \[ \mathrm{HPO_4^{2-} \rightleftharpoons H^+ + PO_4^{3-}} \quad (K_{a3},\ pK_{a3}\approx 12.38) \]

A useful approximation for an aqueous solution containing primarily an amphiprotic species such as H2PO4 is:

\[ \mathrm{pH \approx \tfrac{1}{2}\left(pK_{a1}+pK_{a2}\right)} \approx \tfrac{1}{2}(2.15+7.20)=4.675 \]

The mild acidity reflects the balance between the two tendencies of H2PO4. Proton donation governed by \(K_{a2}\) is typically stronger than proton acceptance governed by \(K_{b} = K_w/K_{a1}\), shifting equilibrium toward pH below 7 for typical concentrations.

Buffer relevance in the phosphate system

Monopotassium phosphate is frequently paired with dipotassium phosphate, K2HPO4, to create a phosphate buffer near neutral pH. The conjugate pair is H2PO4/HPO42−, and the Henderson–Hasselbalch relation applies:

\[ \mathrm{pH = pK_{a2} + \log\!\left(\frac{[HPO_4^{2-}]}{[H_2PO_4^-]}\right)} \]

When \([HPO_4^{2-}] = [H_2PO_4^-]\), the logarithmic term is zero and \(\mathrm{pH \approx p}K_{a2}\), placing the buffer region near \(\mathrm{pH \approx 7.2}\).

Phosphate system predominance diagram (H3PO4, H2PO4−, HPO4^2−, PO4^3−) A horizontal pH axis from 0 to 14 with colored bands showing dominant phosphate species across pH ranges. Vertical markers indicate pKa1, pKa2, and pKa3. The H2PO4− region is emphasized because it is produced by KH2PO4 in water. Dominant phosphate species vs pH (conceptual) 0 2 4 6 8 10 12 14 pH H3PO4 H2PO4 from KH2PO4 HPO42− PO43− pKa1 ≈ 2.15 pKa2 ≈ 7.20 pKa3 ≈ 12.38 Vertical markers show transitions where adjacent species have comparable concentrations.
The colored bands summarize which phosphate form is most prevalent across pH. Dissolution of monopotassium phosphate supplies H2PO4, which sits between the first and second dissociations of phosphoric acid and participates in buffering with HPO42−.

Common confusions and practical notes

  • Monopotassium phosphate (KH2PO4) versus dipotassium phosphate (K2HPO4): different conjugate-base forms and different typical pH ranges in water.
  • “Mono” referring to potassium count, not to the number of acidic hydrogens in the phosphate framework.
  • Phosphate buffering centered near \(pK_{a2}\) rather than near \(pK_{a1}\), reflecting the H2PO4/HPO42− pair.
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