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It might be due to Hamburger's effect( chloride shift). In venous blood, RBC will take up CO2 and CO2 react with water to form carbonic acid ( H2CO3). This acid will then dissociate to form hydrogen ion ( H+) and bicarbonate ion (HCO3-). HCO3- will flow out from RBC and each efflux of HCO3- will be accompanied by influx of Cl-. In some circumstances, some HCO3- and Cl- remain in RBC or maybe the rat eof exchange of HCO3- and Cl- is not the same, and this create water flow into RBC, thus volume of RBC will increase (RBC swells) and hence it's hematocrit value too.

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Q: Why is the hematocrit value of venous blood slightly more than that of arterial blood?
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