Difference in calculated pH and the real pH of a phosphate buffer? I'm from Colombia and I joined this site to ask a question that I could not solve yet. I am calculating the amounts to prepare a phosphate buffer with two salts. I want to prepare a buffer system with pH = 7.0 and a total concentration of Ct = 0.1 M. All my calculations are in the image attached. When I mix the calculated amounts, the obtained pH = 6.5 in the lab. I thought it was my mistake in calculations or an error when I weighed the amounts, but I repeated everything several times and still not get the pH = 7, and the value always was 6.4 or 6.5.

I don't know the reason but I would like to know this. Please help me. I think that If the concentration of the monobasic salt is greather than the dibasic, the pH tends to decrease, but in the calculations the relation [dibasic]/[monobasic] is always less than 1 and this again causes that [monobasic] > [dibasic]. Thanks, I really need a help.
The flaw in your calculations is the assumption that there exists a pK that is a constant independent of concentration.  

In reality, pK is a function of ionic strength.  

At infinite dilution (zero ionic strength) the pK is 7.199 as you assumed.

At 0.1M phosphate concentration, the pK is 6.81.

See Phosphate Buffers which cites to A. A. Green, "The Preparation of Acetate and Phosphate Buffer Solutions of Known PH and Ionic Strength", J. Am. Chem. Soc. 55, 2331, (1933).