Testing ph

Sure, but if it's a single point ph7 calibration, it won't be very accurate.
It's a 2 point calibration and it cost close to 200$
 

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Looks like that should be just fine.
Since a reef tank is between 7.8-8.4, you want to calibrate the zero using ph7, and the 10 for the slope.
As for the why:
In terms of soil or hydroponics if it was acidic, you would use ph 7 and 4 becuase your target is between those 2 points. 7 is always 7 as the constant zero. Just depends if your expected range is going to be above that or below that for which calibration solutions to use. Will almost always be above 7.6 for a marine tank because rocks and sand begin to dissolve at 7.6pH and buffer the water. This is not good and means coral skeleton can dissolve as well.
 
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