Micro-Raman observation on the H2PO4(-) association structures in a supersaturated droplet of potassium dihydrogen phosphate (KH2PO4).

The efflorescence of an individual KH(2)PO(4) droplet on Teflon substrate was investigated by micro-Raman spectroscopy. With the decrease of relative humidity (RH) from 98.0% to 73.0%, the KH(2)PO(4) droplet lost water gradually and entered into supersaturated state, which was reflected by the area ratio between the water stretching band to the sum of ν(s)-PO(2) and ν(s)-P(OH)(2) bands of the H(2)PO(4)(-) (A(H(2)O)/(A((ν(s)-PO(2))+A(ν(s)-P(OH)(2))))). In 1.0 mol l(-1) KH(2)PO(4) solution, the ν(s)-P(OH)(2) and ν(s)-PO(2) bands appeared at 877 and 1077 cm(-1). In the KH(2)PO(4) droplet, the two bands shifted to 894 and 1039 cm(-1) at 98.0% RH, to 899 and 1031 cm(-1) at 89.6% RH, and then to 904 and 997 cm(-1) at 73.0% RH. Moreover, the aggregation process between the H(2)PO(4)(-) ions was observed from the spectral characteristic of the ν(s)-P(OH)(2) band in the concentration process, including the transitions of the H(2)PO(4)(-) ions from monomer in bulk solutions (0.5-1.0 mol l(-1)) to possible dimers at 98.0% RH and then further to oligomers in the droplet with the RH decrease, which were indicated by the blueshift of the ν(s)-P(OH)(2) band and its full width at half-height as a function of the RH. When the RH reached at 72.0%, the anhydrous crystal was obtained. A strong peak appeared at 928 cm(-1), implying that the four oxygen atoms of the H(2)PO(4 (-) were all hydrogen bonding through the bridge hydrogen atoms to get the extensive hydrogen-bonded network structure of the H(2)PO(4)(-) association, leading to the symmetric increase of the H(2)PO(4)(-) ion from C(2v) in dilute solution to quasi-T(d) in the anhydrous crystal.