The CHemical Abundances of Spirals (CHAOS) project leverages the combined power of the Large Binocular Telescope with the broad spectral range and sensitivity of the Multi Object Double Spectrograph (MODS) to measure direct abundances in large samples of HII regions in spiral galaxies. We present LBT MODS observations of 109 Hii regions in NGC5457, of which 74 have robust measurements of key auroral lines, a factor of 3 larger than all previous published detections of auroral lines in the HII regions of NGC5457. Comparing the temperatures derived from the different ionic species we find: (1) strong correlations of T[NII] with T[SIII] and T[OIII], consistent with little or no intrinsic scatter; (2) a correlation of T[SIII] with T[OIII], but with significant intrinsic dispersion; (3) overall agreement between T[NII], T[SII], and T[OII], as expected, but with significant outliers; (4) the correlations of T[NII] with T[SIII] and T[OIII] match the predictions of photoionization modeling while the correlation of T[SIII] with T[OIII] is offset from the prediction of photoionization modeling. Based on these observations, which include significantly more observations of lower excitation HII regions, missing in many analyses, we inspect the commonly used ionization correction factors (ICFs) for unobserved ionic species and propose new empirical ICFs for S and Ar. We have discovered an unexpected population of HII regions with a significant offset to low values in Ne/O, which defies explanation. We derive radial gradients in O/H and N/O which agree with previous studies. Our large observational database allows us to examine the dispersion in abundances, and we find intrinsic dispersions of 0.074 in O/H and 0.095 in N/O (at a given radius). We stress that this measurement of the intrinsic dispersion comes exclusively from direct measurements of HII regions in NGC5457.