Respectfully,
v/q is explained as such.
14% expired o2 refers to the partial pressure of 0.14 in the expired air. Oxygen partial pressure in fresh air is 0.21. so for simplicity, the exchange descreases fresh air by approximately 0.7 of oxygen.

Oxygen saturation in blood refers to places on hemoglobin occupied by oxygen. The saturation is determined by the partial arterial oxygen (dissolved oxygen). The higher the pressure, the closer to 100% hemoglobin saturation can be.
this pressure rises when it is juxtaposed with "fresh air" on alveolar surface to create equilibrium. so the closer the exposures of both sides of the alveolar surface, the better the equilibrium can be. This helps to increase oxygen arterial partial pressure of the blood and subsequently oxygen saturation.

v/q does not mean that for every liter of air in the lungs, there is one liter of blood. The total lung volume is about 5 liters, and blood is about 5 liters as well. But, not all of the blood is in the lungs at one time.

if I misread your question, then ignore my reply.