Understood. Presumably a brick stack in stretcher bond extending a few courses above the roof and whilst the existing capstone is cracked you have examined the brickwork beneath and found it sound. The new capstone should be not less than 75mm thick, be wider than the brickwork by not more than 20mm, and have a 5mm half round or square drip. It should be laid on a DPC of polythene sheet. The mix should be 1 of cement 2 of sand and 4 of aggregate (the agg should be something like 12mm clean stones, no fines or sand). You presumably cannot get a vibrator up there, so it must be well rammed by hand. If you can introduce a mesh of 6mm steel rods in the middle so much the better. Trowel the top of the concrete to fall away from the flue. The flaunching should 1 of cement to 3 of sand with only sufficient water to produce a stiff mix. It is better to bullnose the flaunching rather than come to a feather edge. No additives of any sort are necessary.