Densities, ultrasonic velocity, conductance and viscosity of some alkaline earth metal chlorides such as magnesium chloride (MgCl2) and calcium chloride (CaCl2) were calculated in the concentration range (0.01–0.12 mol kg−1) in 0.01 mol kg−1 aqueous solution of citric acid (CA + H2O) at four varying temperatures T
1 = 303.15 K, T
2 = 308.15 K, T
3 = 313.15 K and T
4 = 318.15 K. The parameters like apparent molar volume (ϕ
v
), limiting apparent molar volume (
ϕ
v
o
${\phi }_{v}^{o}$
) and transfer volume (Δtr
ϕ
v
o
${\phi }_{v}^{o}$
) were calculated from density data. Viscosity data have been employed to calculate Falkenhagen coefficient (A), Jone–Dole’s coefficient (B), relative viscosity (η
r
), and relaxation time (τ) whereas limiting molar conductance (
Λ
m
o
${{\Lambda}}_{m}^{o}$
) has been evaluated from conductance studies. Using these parameters, various type of interactions occurred in the molecules have been discussed. Values of Hepler’s constant (d
2
ϕ
v
o
${\phi }_{v}^{o}$
/dT
2)
p
, (dB/dT) and d(
Λ
m
o
${{\Lambda}}_{m}^{o}$
η
o
)/dT suggests that both MgCl2 and CaCl2 behave as structure breaker in (CA + H2O) system. The positive value of transfer volume exclusively tells about solute–solvent interactions which further indicate that both metal chlorides distort the structure of water and act as structure breaker. These studies are helpful in understanding the nature of interactions occurs in biological systems as CA and metal salts are essential for normal functioning of body.