Monday, September 30, 2019

acid base - Confusion on ion product of water


The ion product of water is defined as $$ K_w = [\ce{H+}][\ce{OH-}] $$ and in pure water $ [\ce{H+}] = [\ce{OH-}]= 1.0 \times 10^{-7}$ and $ K_w = 1.0 \times 10^{-14}$. It is said that if we dissolve some acidic substance in water then $[\ce{H+}]$ will increase and $[\ce{OH-}]$ will decrease and the value of $K_w$ remains constant. I understand that $[\ce{H+}]$ increases because acids donate $\ce{H+}$ (according to Brønsted definition of acids) but how $[\ce{OH-}]$ decreases. I mean a water molecule i.e. $\ce{H2O}$ will certainly break into $\ce{H+}$ and $\ce{OH-}$ and to this $\ce{H+}$ our acid has added it's part and hence it's concentration has increased but why the value of $[\ce{OH-}]$ gets lowered from $1.0 \times 10^{-14}$ , if water molecule were to ionize then whenever $\ce{H+}$ gets formed simultaneously we would get $\ce{OH-}$.



I can cite a common example problem



The concentration of $\ce{OH-}$ ions in a certain household ammonia cleansing solution is $0.0025$. Calculate the concentration of $\ce{H+}$ ions.



We can solve this problem by using the equation $$ K_w = 1.0 \times 10^{-14}$$ $$ [\ce{H+}] [\ce{OH-}] = 1.0 \times 10^{-14}$$ and if put the value of $[\ce{OH-}]$ in the above equation and solve $[\ce{H+}]$, then we would get $ 4.0 \times 10^{-12}$. Here we observe that the value of $[\ce{H+}]$ has decreased from the it's original value in pure water, well this is understandable because ammonia being a base would consume $\ce{H+}$ but how the value of $\ce{OH-}$ has increased.


I want to know that how the chemical reaction can cause the increase or decrease of $\ce{OH-}$ when each molecule of $\ce{H2O}$ always going to yield one $\ce{H+}$ and one $\ce{OH-}$ always.


Thank you. Any help will be much appreciated.



Answer



Another way to look at the problem:


If we add $\ce{H+}$ to the water through adding acid, then some of the $\ce{H+}$ would just remain in the solution as is, and some of them would react with $\ce{OH-}$ in the reaction $\ce{H+ + OH- -> H_2O}$. How much of the added $\ce{H+}$ reacts? To calculate this, you need to know that $\ce{[H+][OH-] = K_w}$ remains constant. So while $\ce{H+}$ is increased, $\ce{OH-}$ is decreased through $\ce{H+ + OH- -> H_2O}$.



If we were to add $\ce{OH-}$ to the water through bases, the same thing would happen: a portion would react with $\ce{H+}$ and a portion would remain in the solution, and it will happen in such a way that is dictated by the constant value of $K_w$.


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